Additive Manufacturing Cartridges And Processes For Producing Cured Polymeric Products By Additive Manufacturing

ABSTRACT

The present disclosure is directed to additive manufacturing cartridges having an oxygen impermeable layer and to processes for producing cured polymeric products by additive manufacturing wherein the oxygen content during additive manufacturing is limited such as by use of the cartridge and/or by use of an inert gas.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No. 16/062,954filed Jun. 15, 2018, assigned U.S. Pat. No. 11,097,531 with an issuedate of Aug. 24, 2021, which claims priority to and benefit of PCTApplication No. PCT/US2016/065360 filed Dec. 7, 2016 which claimspriority to and any other benefit of U.S. Provisional Application Ser.No. 62/268,660 filed Dec. 17, 2015 and entitled “Additive ManufacturingCartridges And Processes For Producing Cured Polymeric Products ByAdditive Manufacturing,” the entire disclosure of each of which ishereby incorporated by reference.

FIELD

The present application is directed to additive manufacturingcartridges, and to processes for producing cured polymeric products byadditive manufacturing.

BACKGROUND

Additive manufacturing (which encompasses processes such as “3DPrinting”) is a process whereby a three-dimensional article ismanufactured (such as by printing) layer by layer from raw material.Certain additive manufacturing processes manufacture an article bybuilding up cross-sectional layers of the article as compared to otherso-called subtractive manufacturing processes which require that certainportions of a manufactured article be removed in order to produce thearticle in its final shape or form. While various additive manufacturingmethods have existed since the 1980s, certain of them have been focusedupon the use of various plastic polymers such as acrylonitrile butadienestyrene (ABS), polycarbonate (PC), high density polyethylene (HDPE), andhigh impact polystyrene (HIPS). Another type of additive manufacturingprocess is roll-to-roll UV-NIL (UV-assisted nanoimprint lithography)which has been used to manufacture various devices including batteryseparators and organic electronics.

SUMMARY

The present disclosure is directed to additive manufacturing cartridgesand to processes for producing cured polymeric products by additivemanufacturing.

In a first embodiment, an additive manufacturing cartridge is disclosed.The cartridge comprises: (a) an actinic radiation curable polymericmixture comprising (i) a polyfunctionalized diene monomer-containingpolymer having the formula: [P][F]n where P represents a diene polymerchain, F represents a functional group, n is 2 to about 15, and each Fcan be the same or different; (ii) optionally a chain extender basedupon F or reactive with F; and (b) an oxygen impermeable layersurrounding (a).

In a second embodiment, a process for producing an additivemanufacturing cartridge according to the first embodiment is disclosed.The process comprises: providing a cartridge having an oxygenimpermeable layer, adding contents comprising (i) and optionally (ii) tothe cartridge to produce an additive manufacturing cartridge with theoxygen impermeable layer surrounding the contents wherein the oxygenlevel of the contents within the oxygen impermeable layer is less than50 ppm.

In a third embodiment, a process for producing a cured polymeric productis disclosed. The process comprises: providing an additive manufacturingdevice comprising a source of actinic radiation, an exterior supportstructure having an atmosphere inside, an interior tank capable ofcontaining a liquid mixture and having an atmosphere above the tank, andan interior support structure; providing to the interior tank a liquidactinic radiation curable polymeric mixture comprising: (i) apolyfunctionalized diene monomer-containing polymer having the formula:[P][F]_(n) where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent; (ii) optionally a chain extender based upon F or reactivewith F; (iii) at least one actinic radiation sensitive photoinitiator;(iv) optionally, a photosensitizer; and (v) a polyfunctional crosslinkerreactive with F; repeatedly forming upon the interior support structurea layer from the liquid mixture; using actinic radiation to cure eachlayer, thereby producing a cured polymeric product. According to thethird embodiment, at least one of the following has an oxygen level ofless than 50 ppm: the liquid actinic radiation curable polymeric mixturewithin the interior tank, the atmosphere above the liquid actinicradiation curable polymeric mixture within the interior tank, theatmosphere surrounding the interior support structure, or the atmosphereinside the exterior support structure.

In a fourth embodiment, a rubber good comprising the cured polymericproduct produced according to the process of the third embodiment isdisclosed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows exemplary closed hollow voids in treads, in cut-awayprofile with the top being the road-contacting surface.

FIG. 2 shows exemplary overhung voids in treads, in cut-away profilewith the top being the road-contacting surface.

FIG. 3 shows exemplary undercut voids in treads, in cut-away profilewith the top being the road-contacting surface.

DETAILED DESCRIPTION

The present disclosure is directed to additive manufacturing cartridgesand to processes for producing cured polymeric products by additivemanufacturing.

In a first embodiment, an additive manufacturing cartridge is disclosed.The cartridge comprises: (a) an actinic radiation curable polymericmixture comprising (i) a polyfunctionalized diene monomer-containingpolymer having the formula: [P][F]n where P represents a diene polymerchain, F represents a functional group, n is 2 to about 15, and each Fcan be the same or different; (ii) optionally a chain extender basedupon F or reactive with F; and (b) an oxygen impermeable layersurrounding (a).

In a second embodiment, a process for producing an additivemanufacturing cartridge according to the first embodiment is disclosed.The process comprises: providing a cartridge having an oxygenimpermeable layer, adding contents comprising (i) and optionally (ii) tothe cartridge to produce an additive manufacturing cartridge with theoxygen impermeable layer surrounding the contents wherein the oxygenlevel of the contents within the oxygen impermeable layer is less than50 ppm.

In a third embodiment, a process for producing a cured polymeric productis disclosed. The process comprises: providing an additive manufacturingdevice comprising a source of actinic radiation, an exterior supportstructure having an atmosphere inside, an interior tank capable ofcontaining a liquid mixture and having an atmosphere above the tank, andan interior support structure; providing to the interior tank a liquidactinic radiation curable polymeric mixture comprising: (i) apolyfunctionalized diene monomer-containing polymer having the formula:[P][F]_(n) where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent; (ii) optionally a chain extender based upon F or reactivewith F; (iii) at least one actinic radiation sensitive photoinitiator;(iv) optionally, a photosensitizer; and (v) a polyfunctional crosslinkerreactive with F; repeatedly forming upon the interior support structurea layer from the liquid mixture; using actinic radiation to cure eachlayer, thereby producing a cured polymeric product. According to thethird embodiment, at least one of the following has an oxygen level ofless than 50 ppm: the liquid actinic radiation curable polymeric mixturewithin the interior tank, the atmosphere above the liquid actinicradiation curable polymeric mixture within the interior tank, theatmosphere surrounding the interior support structure, or the atmosphereinside the exterior support structure.

In a fourth embodiment, a rubber good comprising the cured polymericproduct produced according to the process of the third embodiment isdisclosed.

Definitions

The terminology as set forth herein is for description of theembodiments only and should not be construed as limiting the inventionas a whole.

As used herein, the phrase “oxygen impermeable” refers to a material (orlayer) having an oxygen transmission rate (OTR) of less than 150cc/m²·day·atmosphere. The units can alternatively be stated as cm³/m²over 24 hours (i.e., 1 day) and 1 atmosphere and refer to thetransmission of oxygen through a sample of material over the course of24 hours, at 1 atmosphere of pressure, 23° C. and 0% relative humidity(RH). As those of skill in the art will appreciate, the particular OTRof a layer will generally vary depending upon the thickness of materialused in the layer. An oxygen impermeable layer is intended to encompasslayers of varying materials and thickness so long as the OTR providedabove is met.

As used herein, the phrase “actinic radiation” refers to electromagneticradiation capable of producing photochemical reactions.

As used herein, the phrase “additive manufacturing” refers to theprocess of joining materials to make objects from 3D model data, usuallylayer upon layer, as opposed to subtractive manufacturing methodologies.

As used herein, the term “cartridge” refers to a container that isadapted for or configured for use in an additive manufacturing device.

As used herein, the phrase “chain extender” refers to amonofunctionalized hydrocarbon or hydrocarbon derivative containing afunctional group that reacts with a functional end group of the dienepolymer chain and adds to the polymer chain, thereby increasing itsmolecular weight.

As used herein, the phrase “polyfunctional crosslinker” refers to ahydrocarbon or hydrocarbon derivative containing two or more functionalgroups which are capable of undergoing a reaction to providecross-linking between two diene polymer chains or within a diene polymerchain.

As used herein, the term “hydrocarbon” refers to a compound consistingentirely of carbon and hydrogen atoms.

As used herein, the phrase “hydrocarbon derivative” refers to ahydrocarbon containing at least one heteroatom (e.g., N, O, S).

As used herein, the term “mer” or “mer unit” means that portion of apolymer derived from a single reactant molecule (e.g., ethylene mer hasthe general formula —CH2CH2-).

As used herein, the term “(meth)acrylate” encompasses both acrylate andmethacrylate.

As used herein, the term “photoinitiator” refers to a compound thatgenerates free radicals. The term “photoinitiator” is usedinterchangeably herein with the phrase “actinic radiation sensitivephotoinitiator.”

As used herein, the term “photosensitizer” refers to a light absorbingcompound used to enhance the reaction of a photoinitiator. Uponphotoexcitation, a photosensitizer leads to energy or electron transferto a photoinitiator.

As used herein, the term “polyfunctionalized” refers to more than onefunctionalization and includes polymers that have beendi-functionalized, tri-functionalized, etc. Generally, functionalizationof a polymer may occur at one or both ends of a polymer chain, along thebackbone of the polymer chain, in a side chain, and combinationsthereof.

As used herein, the term “polymer” refers to the polymerization productof two or more monomers and is inclusive of homo-, co-, ter-,tetra-polymers, etc. Unless indicated to the contrary herein, the termpolymer includes oligomers.

As used herein, the term “void” refers to a portion of a tire tread thatis devoid of material (other than air); the term can include grooves orchannels extending around all or a portion of the circumference of thetire as well as a pocket or cavity that does not extend around thecircumference of the tire.

Additive Manufacturing Cartridge

As discussed above, the first embodiment disclosed herein is directed toan additive manufacturing cartridge. The cartridge comprises: (a) anactinic radiation curable polymeric mixture comprising (i) apolyfunctionalized diene monomer-containing polymer having the formula:[P][F]n where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent; (ii) optionally a chain extender based upon F or reactivewith F; and (b) an oxygen impermeable layer surrounding (a). As furtherdiscussed above, the additive manufacturing cartridge is a containeradapted or configured for use in an additive manufacturing device. Othertypes of containers such as may be useful for shipping or storage canoptionally be included as part of the overall cartridge. As alsodiscussed above, the processes of the second embodiment includeproviding a cartridge having an oxygen impermeable layer. Certainembodiments of the processes of the third embodiment (i.e., forproducing a cured polymeric product) will include the use of a cartridgehaving an oxygen impermeable layer. For convenience, aspects of thecartridges of the first-third embodiments are discussed together hereinand the following discussion should be understood to apply to any andall of those embodiments unless indicated to the contrary. In certainembodiments of the first-third embodiments, the actinic radiationcurable mixture includes the chain extender in the actinic radiationcurable polymeric mixture. In certain embodiments of the first-thirdembodiments disclosed herein, the actinic radiation curable polymericmixture further comprises (includes): (iii) at least one actinicradiation sensitive photoinitiator; (iv) optionally, a photosensitizer;and (v) a polyfunctional crosslinker reactive with F. In certainembodiments of the first-third embodiments, the actinic radiationcurable mixture includes the photosensitizer.

Generally, the additive manufacturing cartridge can be understood asconstituting a package capable of enclosing the contents, i.e., theactinic radiation curable polymeric mixture. According to thefirst-third embodiments, the shape of the additive manufacturingcartridge may vary; generally the cartridge will be adapted to fit intoan additive manufacturing device and/or configured to be removablysecured to a printer head (or other device within the additivemanufacturing device adapted to dispense the content of the cartridge)of the additive manufacturing device. In certain embodiments of thefirst-third embodiments, the additive manufacturing cartridge comprises(includes) an opening adapted to interface with the printer head of theadditive manufacturing device and allow flow of the actinic radiationcurable polymeric mixture into the printer head for use in forminglayers and ultimately a cured polymeric product.

In certain embodiments of the first-third embodiments disclosed herein,the additive manufacturing cartridge comprises at least two separatecompartments. In certain such embodiments, a first compartment contains(i) (i.e., polyfunctionalized diene monomer-containing polymer havingthe formula [P][F]n where P represents a diene polymer chain, Frepresents a functional group, n is 2 to about 15, and each F can be thesame or different) and when present (ii) (i.e., a chain extender basedupon F or reactive with F); and a second compartment contains at leastone of (iii) or (iv) (i.e., at least one actinic radiation sensitivephotoinitiator or a photosensitizer, respectively), when present (v)(i.e., polyfunctional crosslinker reactive with F), and when present atleast a portion of (ii).

Various combinations of one or more compartments for the cartridgesaccording to the first-third embodiments disclosed herein are envisionedto contain the ingredients of the actinic radiation curable polymericmixture in its various sub-embodiments (as described below). In certainembodiments of the first-third embodiments, at least two cartridges (orcompartments) are utilized, with cartridge or compartment comprising:the polyfunctionalized diene monomer-containing polymer having theformula [P][F]_(n) where P represents a diene polymer chain, Frepresents a functional group, n is 2 to about 15, and each F can be thesame or different and chain extender based upon F or reactive with F andthe second cartridge or compartment comprising chain extender based uponF or reactive with F along with at least one of an actinic radiationsensitive photoinitiator and a photosensitizer. In certain of theforegoing embodiments, the second cartridge or compartment furthercomprises a crosslinker reactive with F; alternatively, a thirdcartridge or compartment comprising a crosslinker reactive with F can beprovided. In certain embodiments, a kit is provided for producing anelastomeric cured product by additive printing comprising at least twocartridges as previously described. In certain embodiments, the kitcomprises at least two cartridges, wherein at least one cartridgecomprises a polyfunctionalized diene monomer-containing polymer havingthe formula [P][F]_(n) where P represents a diene polymer chain, Frepresents a functional group, n is 2 to about 15, and each F can be thesame or different and a chain extender based upon F or compatible withF; and at least a cartridge comprises a chain extender based upon F orcompatible with F, at least one of an actinic radiation sensitivephotoinitiator and a photosensitizer, and optionally a crosslinkerreactive with F. In certain of the foregoing embodiments of the kit andcartridges, at least one of the first or second cartridge or compartmentfurther comprises at least one filler (as discussed in more detailbelow).

Oxygen Impermeable Layer

As discussed above, the additive manufacturing cartridge of the firstembodiment disclosed herein comprises (includes) an oxygen impermeablelayer surrounding the actinic radiation curable polymeric mixturecontents of the cartridge. As also discussed above, the processes of thesecond embodiment include providing a cartridge having an oxygenimpermeable layer. Certain embodiments of the processes of the thirdembodiment (i.e., for producing a cured polymeric product) will includethe use of a cartridge having an oxygen impermeable layer. Forconvenience, the oxygen impermeable layer of the first-third embodimentsare discussed together herein and the following discussion should beunderstood to apply to any and all of those embodiments unless indicatedto the contrary. By surrounding the actinic radiation curable polymericmixture, the oxygen impermeable layer serves to protect those contentsfrom oxygen during shipping, storage and use.

The oxygen impermeable layer may be made of one or more than onematerial. When more than one material is utilized, the materials may belayered in various configurations and relative thicknesses, may be mixedtogether in a type of composite mixture, or may be blended together intoone homogenous mixture. The particular material or materials of whichthe oxygen impermeable layer is comprised may vary. In certainembodiments of the first-third embodiments, the oxygen impermeable layercomprises one or more metals, glass, one or more polymers, or acombination thereof. Non-limiting examples of suitable metals that canbe utilized in the oxygen impermeable layer of certain embodiments ofthe first-third embodiments, include, but are not limited to, aluminumfoil, tin foil, copper foil, or a combination thereof. As used herein,the term foil is intended to refer to a metal sheet having a thicknessof less than 0.2 mm. Non-limiting examples of suitable polymers that canbe utilized in the oxygen impermeable layer of certain embodiments ofthe first-third embodiments include: ethylene-vinyl alcohol copolymer(EVOL), polyvinyl alcohol (PVA, PVOH or PVAI), polyesters (e.g.,polyethylene terephthalate or PET, glycol-modified PET, acid-modifiedPET, poly(ethylene-2,6-naphthalate) or PEN, polybutylene terephthalateor PBT, polytrimethylterephthalate or PTT), polyvinyl chloride polymer(PVC), vinyl chloride copolymer, vinylidene chloride polymer,polyvinylidene chloride (PVdC), polyvinylidene fluoride (PVdF),polyvinylpyridines, polyamines, acrylate polymers (e.g., polyacrylicacid, polyacrylonitrile, polymethacrylic acid, poly(methyl methacrylate,polyacrylamide, polyacrylonitrile), cellulose derivative polymers(carboxyalkylcellulose, hydroxyethylcellulose, hydroxypropylcellulose,hydroxypropylmethyl cellulose), chitosan, polyamines, polyethyleneoxide, ethylene vinyl acetate copolymer, and combinations thereof. Incertain embodiments of the first-third embodiments, the oxygenimpermeable layer comprises ethylene-vinyl alcohol copolymer (EVOH). Incertain embodiments of the first-third embodiments, the oxygenimpermeable layer comprises at least two layers with at least one ofthose layers comprising a polymer and at least one layer comprising ametal foil; in certain such embodiments the polymer comprises EVOH andthe metal foil comprises aluminum, tin, copper, or a combinationthereof. In certain embodiments of the first-third embodiments disclosedherein, the oxygen impermeable layer is flexible in that it is capableof at least partially deforming or collapsing upon evacuation or itscontents. In certain embodiments of the first-third embodimentsdisclosed herein, the oxygen impermeable layer is surrounded by a rigidouter container; the rigid outer container may be useful to protect thecartridge during shipping and storage and may be removable prior to useof the cartridge with an additive manufacturing device. The rigid outercontainer may or may not be comprised of an oxygen impermeable material.In certain embodiments of the first-third embodiments disclosed herein,the oxygen impermeable layer is flexible and is surrounded by a rigidouter container.

In certain embodiments of the first-third embodiments disclosed herein,the oxygen impermeable layer includes one or more fillers whichcontribute to (increase) the oxygen impermeability of the layer.Non-limiting examples of such fillers include one or more of: calciumcarbonate, clay, talc, alumina, magnesium carbonate, or mica. Preferablywhen a filler is used, it is incorporated into one or more of thepolymers, as discussed above.

As discussed above, the oxygen impermeable layer of the first embodimentand the oxygen impermeable layer according to certain embodiments of thefirst and second embodiments will be comprised of a material having anoxygen transmission rate (OTR) of less than 150 cc/m²·day·atmosphere.The units can alternatively be stated as cm³/m² over 24 hours (i.e., 1day) and 1 atmosphere and refer to the transmission of oxygen through asample of material (or sample of the layer) over the course of 24 hours,at 1 atmosphere of pressure, 23° C. and 0% relative humidity (RH). Asthose of skill in the art will appreciate, the particular OTR of amaterial or layer will generally vary depending upon the thickness ofmaterial(s) used and the overall thickness of the layer. An oxygenimpermeable layer is intended to encompass layers of varying materialsand thickness so long as the OTR provided above is met. In certainembodiments of the first-third embodiments, the oxygen impermeable layerhas an OTR of less than 150 cc/m²·day·atmosphere (e.g., 150, 145, 140,135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60,55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.1, 0.01, 0.001cc/m²·day·atmosphere), including less than 140 cc/m²·day·atmosphere,less than 130 cc/m²·day·atmosphere, less than 120 cc/m²·day·atmosphere,less than 110 cc/m²·day·atmosphere, less than 100 cc/m²·day·atmosphere,less than 90 cc/m²·day·atmosphere, less than 80 cc/m²·day·atmosphere,less than 70 cc/m²·day·atmosphere, less than 60 cc/m²·day·atmosphere,less than 50 cc/m²·day·atmosphere, less than 40 cc/m²·day·atmosphere,less than 30 cc/m²·day·atmosphere, less than 20 cc/m²·day·atmosphere,less than 10 cc/m²·day·atmosphere, less than 5 cc/m²·day·atmosphere, orless than 1 cc/m²·day·atmosphere. An OTR value can be determined byvarious standardized method and the values referred to herein areintended to refer to and encompass values determined by ASTM methodD3895 and ASTM method F1927.

In certain embodiments of the first-third embodiments disclosed herein,the additive manufacturing cartridge comprises at least two separatecompartments. In certain such embodiments, a first compartment contains(i) (i.e., polyfunctionalized diene monomer-containing polymer havingthe formula [P][F]n where P represents a diene polymer chain, Frepresents a functional group, n is 2 to about 15, and each F can be thesame or different) and when present (ii) (i.e., a chain extender basedupon F or reactive with F); and a second compartment contains at leastone of (iii) or (iv) (i.e., at least one actinic radiation sensitivephotoinitiator or a photosensitizer, respectively), when present (v)(i.e., polyfunctional crosslinker reactive with F), and when present atleast a portion of (ii).

In certain embodiments of the first-third embodiments disclosed herein,the oxygen level of the contents contained within the additivemanufacturing cartridge (i.e., within the oxygen impermeable layer) isless than 50 ppm (e.g., 49 ppm, 45 ppm, 40 ppm, 35 ppm, 30 ppm, 25 ppm,20 ppm, 15 ppm, 10 ppm, 5 ppm, 1 ppm, or less), including less than 40ppm, less than 30 ppm, less than 20 ppm, or less than 10 ppm. Asdiscussed below, various methods exist for limiting the oxygen contentof the contents within the cartridge so as to achieve these levelsincluding, but not limited to, reducing the oxygen content of thecontents by subjecting them to vacuum and/or adding an inert gas to thecartridge prior to adding the contents to the cartridge. According tothe foregoing methods, in certain such embodiments, the pressure insidethe cartridge will be greater than the ambient pressure (i.e., thepressure outside the cartridge) based upon the addition of an inert gasto the cartridge, in order to reduce the oxygen content prior to addingthe contents to the cartridge. Various inert gases such as nitrogen,argon, helium, carbon dioxide, and combinations thereof may be utilizedin various embodiments of the first-third embodiments. In certainembodiments of the first-third embodiments the inert gas comprisesnitrogen.

Processes for Producing an Additive Manufacturing Cartridge

As discussed above, the second embodiment disclosed herein is directedto a process for producing an additive manufacturing cartridge accordingto the first embodiment. The process comprises: providing a cartridgehaving an oxygen impermeable layer, adding contents comprising (i) andoptionally (ii) to the cartridge to produce an additive manufacturingcartridge with the oxygen impermeable layer surrounding the contentswherein the oxygen level of the contents within the oxygen impermeablelayer is less than 50 ppm. The cartridge of the second embodiment shouldbe understood to include all of the options and variations as discussedabove for the cartridge of the first embodiment. The oxygen impermeablelayer of the cartridge constitutes a package capable of enclosing thecontents, i.e., the actinic radiation curable polymeric mixture.

In certain embodiments of the second embodiment, the process furthercomprises adding an inert gas to the cartridge prior to adding thecontents to the cartridge. Various inert gases such as nitrogen, argon,helium, carbon dioxide, and combinations thereof may be utilized invarious embodiments of the processes of the second embodiment. Incertain embodiments of the second embodiment the inert gas comprisesnitrogen. In certain embodiments of the second embodiment, prior toadding the contents to the cartridge, the oxygen level within thecartridge is less than 50 ppm (e.g., 49 ppm, 45 ppm, 40 ppm, 35 ppm, 30ppm, 25 ppm, 20 ppm, 15 ppm, 10 ppm, 5 ppm, 1 ppm, or less), includingless than 40 ppm, less than 30 ppm, less than 20 ppm, or less than 10ppm. In certain embodiments of the second embodiment, the oxygen levelof the contents is reduced to one of the foregoing levels prior toadding the contents to the cartridge; in certain such embodiments, theoxygen level is reduced by subjecting the contents to a vacuum.

Actinic Radiation Curable Polymeric Mixture

As discussed above, the first-third embodiments disclosed herein contain(or make use of) an actinic radiation curable polymeric mixturecomprising (a) a polyfunctionalized diene monomer-containing polymerhaving the formula: [P][F]_(n) where P represents a diene polymer chain,F represents a functional group, n is 2 to about 15, and each F can bethe same or different; (b) optionally a chain extender based upon F orreactive with F; (c) at least one actinic radiation sensitivephotoinitiator; (d) optionally, a photosensitizer; and (e) apolyfunctional crosslinker reactive with F. Generally, the actinicradiation curable polymeric mixture is suitable for use in additivemanufacturing processes which utilize various additive manufacturingdevices. The product or article produced by curing the actinic radiationcurable polymeric mixture is referred to herein as a curedelastomeric/polymeric product. In certain embodiments according to thefirst-third embodiments, the actinic radiation curable polymeric mixtureis curable by light having a wavelength in the UV to Visible range. Incertain embodiments of the first-third embodiments, the actinicradiation (light) has a wavelength of about 320 to less than 500 nm,including about 350 to about 450 nm, and about 365 to about 405 nm.Generally, there are two types of radiation induced curing chemistries:free radical and cationic. Free radical curing involves cross-linkingthrough double bonds, most usually (meth)acrylate double bonds. Cationiccuring involves cross-linking through other functional groups, mostusually epoxy groups.

Polyfunctionalized Diene Monomer-Containing Polymer

As discussed above, according to the first-third embodiments disclosedherein, the actinic radiation curable polymeric mixture comprises apolyfunctionalized diene monomer-containing polymer which comprises adiene polymer chain [P]. In certain embodiments of the first-thirdembodiments, the actinic radiation curable polymeric mixture comprisesone type of polyfunctionalized diene monomer-containing polymer and inother embodiments, the mixture comprises more than one type ofpolyfunctionalized diene monomer-containing polymer. Polyfunctionalizeddiene monomer-containing polymers can be categorized into differenttypes based upon one or more of: molecular weight, monomer type(s),relative amount of monomer(s), types of functional group(s) (e.g., freeradical polymerizable or cationic polymerizable), identity of functionalgroup(s) (as discussed in more detail below), and amount of functionalgroup(s). In certain embodiments of the first-third embodiments, thepolyfunctionalized diene monomer-containing polymer(s) can be referredto as a pre-polymer since they will react with each other and with achain extender (when a chain extender is present) to form a highermolecular weight polymer. The diene polymer chain comprises (is basedupon) at least one diene monomer. A diene monomer is a monomer havingtwo carbon-carbon double bonds. Various diene monomers exist and aregenerally suitable for use in preparing the diene polymer chain of thepolyfunctionalized diene monomer-containing polymer. In certainembodiments according to the first-third embodiments disclosed herein,the diene polymer chain of the polyfunctionalized dienemonomer-containing polymer comprises monomers selected from at least oneof: acyclic and cyclic diener having 3 to about 15 carbon atoms. Incertain embodiments according to the first-third embodiments disclosedherein, the diene polymer chain of the polyfunctionalized dienemonomer-containing polymer comprises monomers selected from at least oneof: 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene,2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene,2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, 2,4-hexadiene, 1,3-cyclopentadiene,1,3-cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene,farnescene, and substituted derivatives of each of the foregoing. Incertain embodiments of the first-third embodiments, the diene polymerchain of the polyfunctionalized diene monomer-containing polymercomprises 1,3-butadiene monomer, isoprene monomer, or a combinationthereof. In certain embodiments of the first-third embodiments, thediene polymer chain of the polyfunctionalized diene-monomer-containingpolymer further comprises at least one vinyl aromatic monomer.Non-limiting examples of suitable vinyl aromatic monomers include, butare not limited to, styrene, α-methyl styrene, p-methylstyrene,o-methylstyrene, p-butylstyrene, vinylnaphthalene, p-tertbutylstyrene,vinyl catechol-based, and combinations thereof. In certain embodimentsof the first-third embodiments, the diene polymer chain of thepolyfunctionalized diene monomer-containing polymer comprises acombination of 1,3-butadiene monomer and styrene monomer.

As discussed above, the term “polyfunctionalized” is used herein torefer to more than one functionalization and includes polymers that havebeen di-functionalized, tri-functionalized, etc. Generally,functionalization of a polymer may occur at one or both ends of apolymer chain, along the backbone of the polymer chain, and combinationsthereof. Generally, each F functional group present in thepolyfunctionalized diene monomer-containing polymer may be same ordifferent. In certain embodiments according to the first-thirdembodiments disclosed herein, the polyfunctionalized dienemonomer-containing polymer comprises a di-functionalized polymer havingan F functional group at each terminal end of the polymer chain; each Ffunctional group may be the same or different. In certain embodimentsaccording to the first-third embodiments disclosed herein, thepolyfunctionalized diene monomer-containing polymer comprises adi-functionalized polymer having a F functional group at one terminalend of the polymer chain and at least one additional F functional groupalong the backbone of the polymer chain; each F functional group may bethe same or different. In certain embodiments according to thefirst-third embodiments disclosed herein, the polyfunctionalized dienemonomer-containing polymer comprises a functionalized polymer having atleast three F functional groups, with one at each terminal end of thepolymer chain, and at least one along the backbone of the polymer chain;each F functional group may be the same or different.

Various polyfunctionalized diene monomer-containing polymers arecommercially available and may be suitable for use in variousembodiments of the first-third embodiments disclosed herein.Non-limiting examples of these include, but are not limited to, SartomerCN307 polybutadiene dimethacrylate, Sartomer CN301 polybutadienedimethacrylate and Sartomer CN303 hydrophobic acrylate ester, allavailable from Sartomer Americas (Exton, Pa.); Ricacryl® 3500methacrylated polybutadiene, Ricacryl® 3801 methacrylated polybutadiene,Ricacryl® 3100 methacrylated polybutadiene, all available from CrayValley USA LLC (Exton, Pa.); BAC-45 polybutadiene diacrylate and BAC-15polybutadiene diacrylate, available from San Esters Corp. (New York,N.Y.); Kuraray UC-102 methacrylated polyisoprene and UC-203methacrylated polyisoprene, available from Kuraray America Inc.(Pasadena, Tex.); Poly bd® 600E epoxidized polybutadiene and Poly bd°605E polybutadiene, available from Cray Valley USA LLC (Exton, Pa.).Methods for preparing polyfunctionalized diene monomer-containingpolymers are well-known to those of skill in the art and include thoseusing functional initiators, functional terminators and reactions ofdiol terminated diener with various functional acid chlorides or withcarboxylic acids (through a dehydration reaction). Other methods includethe reaction of an oxidant and a carboxylic acid to form a peracid foradding an epoxy group.

In certain embodiments of the first-third embodiments, the diene polymerchain of the polyfunctionalized diene monomer-containing polymercomprises: polybutadiene, styrene-butadiene copolymer, polyisoprene,ethylene-propylene-diene rubber (EPDM), styrene-isoprene rubber, orbutyl rubber (halogenated or non-halogenated).

The molecular weight of the polyfunctionalized diene monomer-containingpolymer according to the first-third embodiments may vary widelydepending upon various factors, including, but not limited to the amountand type of chain extender (if any) that is utilized in the actinicradiation curable polymeric mixture. Generally, higher molecular weightpolymers will lead to better properties in the cured article or product,but will also lead to higher viscosities in the overall actinicradiation curable polymeric mixture. Thus, preferred polyfunctionalizeddiene monomer-containing polymers for use in the mixture will balancemolecular weight with its effect on viscosity. In certain embodiments ofthe first-third embodiments, the polyfunctionalized dienemonomer-containing polymer has a Mn of about 3,000 to about 135,000grams/mole (polystyrene standard). In certain embodiments of thefirst-third embodiments, the polyfunctionalized diene monomer-containingpolymer has a Mn of 3,000 to 135,000 grams/mole (polystyrene standard);including about 5,000 to about 100,000 grams/mole (polystyrenestandard); 5,000 to 100,000 grams/mole (polystyrene standard); about10,000 to about 75,000 grams/mole (polystyrene standard); and 10,000 to75,000 grams/mole (polystyrene standard). The number average molecularweights (M_(n)) values that are discussed herein for thepolyfunctionalized diene monomer-containing polymer include the weightcontributed by the functional groups (F).

In certain embodiments of the first-third embodiments, the curedelastomeric mixture comprises crosslinked polyfunctionalized dienemonomer-containing polymer has a Mc (molecular weight betweencrosslinks) of about 500 to about 150,000 grams/mole, including 500 to150,000 grams/mole (e.g., 1000, 2500, 5000, 10000, 20000, 25000, 30000,40000, 50000, 60000, 70000, 80000, 90000, 100000, 110000, 115000,120000, 130000, 140000 or 150000). The crosslinked molecular weight(M_(c)) values that are discussed herein for the polyfunctionalizeddiene monomer-containing polymer include the weight contributed by thefunctional groups (F). M_(c) can be determined in accordance withpreviously published procedures such as those disclosed in Hergenrother,J., Appl. Polym. Sci., v. 32, pp. 3039 (1986), herein incorporated byreference in its entirety.

In certain embodiments of the first-third embodiments, the molecularweight of the crosslinked polyfunctionalized diene monomer-containingpolymer of the cured elastomeric mixture can be quantified in terms ofM_(r) or molecular weight between chain restrictions. In certainembodiments of the first-third embodiments, the cured elastomericmixture comprises crosslinked polyfunctionalized dienemonomer-containing polymer has a Mc (molecular weight betweencrosslinks) of about 500 to about 150,000 grams/mole, including 500 to150,000 grams/mole (e.g., 1000, 2500, 5000, 10000, 20000, 25000, 30000,40000, 50000, 60000, 70000, 80000, 90000, 100000, 110000, 115000,120000, 130000, 140000 or 150000). The crosslinked molecular weight(M_(c)) values that are discussed herein for the polyfunctionalizeddiene monomer-containing polymer include the weight contributed by thefunctional groups (F). Generally M_(r) can be determined according tothe procedure described in U.S. Patent Application Publication No.2012/0174661, herein incorporated by reference in its entirely. Morespecifically, M_(r) can be determined according to the followingequation:

$M_{r} = \frac{\rho\;{{RT}\left( {⩓ {- ⩓^{- 2}}} \right)}}{\sigma}$

where ρ is the compound density, σ is stress, R is the gas constant, Tis temperature, Λ is 1+Xϵ where X is the strain amplification factorfrom the Guth-Gold equation and the strain (ϵ) is (l−l_(set))/l_(set)where l is the specimen length at a point on the retraction curve andl_(set) is the specimen length after retraction to zero stress. A TR ortensile retraction test set consists of at least two tensile retractiontests, each to a progressively higher target extension ratio, Amax,followed immediately by a retraction to a zero stress. Each tensile pulland subsequent retraction are performed at the same testing rate suchthat a series of extension and retraction curve pairs are obtained.During each retraction, the stress, σ, is measured as a function ofextension ratio, Λ, defining the tensile retraction curve. Testing maybe performed in accordance with the procedures outlined in Hergenrother,J., Appl. Polym. Sci., v. 32, pp. 3039 (1986), herein incorporated byreference in its entirety.

When determining M_(r) for compounds containing rigid fillers, theenhancement of modulus due to rigid particles should be taken intoaccount in a fashion similar to that of Harwood and Payne, J. Appl.Polym. Sci., v. 10, pp. 315 (1966) and Harwood, Mullins and Payne, J.Appl. Polym. Sci, v. 9, pp. 3011 (1965), both of which are hereinincorporated by reference in their entirety. When a filled compound isfirst stretched in tension to the same stress as its corresponding gumcompound (e.g., non-filled compound), subsequent retraction andextension curves are generally very similar to those of the gumcompounds when stress is graphed as a function of normalized strain.Normalized strain is defined as the strain at any point on thesubsequent extension or retraction curves divided by the maximum strainof the initial extension. For retraction curves in particular, and formaximum strains of natural rubber gum compounds up to and including nearbreaking strain, this could be applied to a number of filled compounds.The result can be interpreted as evidence of strain amplification of thepolymer matrix by the filler, where the average strain the polymermatrix of a filled compound is the same as that in the corresponding gum(non-filled) compound, when the filled and gum compounds are compared atthe same stress. Strain amplification X can be determined by theGuth-Gold equation as discussed in Mullins et al., J. Appl. Polym. Sci.,vol. 9, pp. 2993 (1965) and Guth et al., Phys. Rev. v. 53, pp. 322(1938), both of which are herein incorporated by reference in theirentirety. After correction of A for filler level, neo-Hookean rubberelasticity theory (Shen, Science & Technology of Rubber, Academic Press,New York, 1978, pp. 162-165, herein incorporated by reference) may beapplied to an internal segment of the retraction curve from which amolecular weight between chain restrictions of all types, M_(r) can becalculated according to the above equation. Extension of the same rubberspecimen to successively higher Amax provides M_(r) as a function ofAmax.

Tensile retraction testing can be measured using a special ribbed TRmold to prevent slippage when stretched in tension between clamps of anInstron 1122 tester controlled by a computer (for testing, dataacquisition and calculations), as described in Hergenrother, J., Appl.Polym. Sci., v. 32, pp. 3039 (1986). Specimens for testing may benominally 12 mm wide by 50 mm long by 1.8 mm thick. M_(r) can becalculated at each of 25 (σ, Λ) pairs, collected from about the middleone-third of the particular retraction curve. M_(r) values as disclosedherein may be the average of the 25 calculated values. In order toreduce test time, elongations to successively higher Λmax can be carriedout at successively higher speeds of the Instron crosshead motion. Amaster TR curve can be obtained by shifting the different test speeds toa standardized testing rate of 5%/minute. High strain (greater thanabout 40% to 80% elongation) region of the smooth curve obtained may befitted by a linear equation of the form of M_(r)=S(Λmax−1)+Mc. The fitto strain region at less than 80% elongation may deviate steadily fromthe M_(r) line as strains are progressively reduced. The logarithm ofsuch difference between the calculated and observed νe can be plottedversus the lower level of strain to give a linear fit to Δve as afunction of (Λmax−1). The antilog of the reciprocal of the intercept, m,can be denoted as B (expressed in kg/mole) and relates to themicro-dispersion of the filler. See, U.S. Pat. No. 6,384,117, hereinincorporated by reference in its entirety. In a similar fashion, thelowest strain deviation can be treated to give a plot of ΔΔve as afunction of (Λmax−1). The antilog of the reciprocal of the intercept forthe process that occurs at strains of less than 6% elongation can bedenoted as y (expressed in kg/mole). These three equations, each with aslope and intercept, can be used to fit the various strain regions ofthe TR curve can be summed to provide a single master equation thatempirically describes the M_(r) response over the entire range oftesting. Experimental constants of the new master equation can beadjusted using ExcelSolver® to obtain the best possible fit of thepredicted values to the experimental values obtained by TR. Fittingcriteria consisting of a slope and an intercept can be determined whenthe experimental and curve fit values of M_(r) are compared. Thecomposite equation can allow the transition between each fitted linearregion to be independent of the choice of the experimental strainsmeasured and the small mathematical adjusting of the strain range canallow a more precise linear fit of the data to be made.

F Functional Groups

As discussed above, F represents a functional group associated with thepolyfunctionalized diene monomer-containing polymer. Various types offunctional groups F may be suitable for use in certain embodiments ofthe first-third embodiments disclosed herein. In certain embodiments ofthe first-third embodiments, these functional groups F can be describedas either free radical polymerizable or cationic polymerizable, which isa general description of how the groups react upon exposure to actinicradiation (light) to result in cross-linking or curing. Generally,functional groups that improve curability (cross-linking) by actinicradiation are useful as the functional group F.

In certain embodiments of the first-third embodiments, the F functionalgroup of the polyfunctionalized diene monomer-containing polymercomprises a free radical polymerizable functionalizing group. In certainembodiments of the first-third embodiments, the F functional group ofthe polyfunctionalized diene monomer-containing polymer comprises acationic polymerizable functionalizing group. In certain embodiments ofthe first-third embodiments, the F functional group of thepolyfunctionalized diene monomer-containing polymer comprises acombination of cationic polymerizable and free radical polymerizablefunctional groups either on the same diene polymer chain or on separatediene polymer chains. Generally, functional groups that are free radicalpolymerizable have the advantage of reacting faster than cationicpolymerizable functionalizing groups, but the disadvantage is beingprone to inhibition by oxygen exposure. Generally, functional groupsthat are cationic polymerizable have the advantage of being resistant tooxygen exposure (i.e., they are not inhibited), but have thedisadvantages of being prone to inhibition by water exposure and havinga generally slower rate of reaction. The combination of cationicpolymerizable and free radical polymerizable functional groups can beadvantageous as providing the advantages of each type and minimizing thedisadvantages of each alone; an additional advantage of such acombination is to allow for a double network system wherein a crosslinkof a first type occurs at a first wavelength and a crosslink of a secondtype occurs at a second wavelength or a single wavelength is used toactivate both types of photoinitiators which will create a doublenetwork.

In certain embodiments of the first-third embodiments, each functionalgroup F in the polyfunctionalized diene monomer-containing polymercomprises at least one of: acrylate, methacrylate, cyanoacrylate,epoxide, aziridine, and thioepoxide. In certain embodiments of thefirst-third embodiments, each functional group F in thepolyfunctionalized diene monomer-containing polymer comprises anacrylate or methacrylate. Suitable acrylates or methacrylates may belinear, branched, cyclic, or aromatic. As used herein, the term acrylateshould be understood to include both acrylic acid and esters thereof.Similarly, the term methacrylate should be understood to include bothmethacrylic acid and esters thereof. Various types of acrylates andmethacrylates are commonly used and may be suitable for use as thefunctional group F. In certain embodiments of the first-thirdembodiments disclosed herein, the function group F comprises at leastone of: acrylic acid, methacrylic acid, ethyl (meth)acrylate, methyl(meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate,cyclobutyl (meth)acrylate, (cyano)acrylate, 2-ethylhexyl(meth)acrylate,isostearyl (meth)acrylate, isobornyl (meth)acrylate, propyl(meth)acrylate, isopropyl (meth)acrylate, cyclopropyl (meth)acrylate,pentyl (meth)acrylate, isopentyl (meth)acrylate, cyclopentyl(meth)acrylate, hexyl (meth)acrylate, isohexyl (meth)acrylate,cyclohexyl (meth)acrylate, heptyl (meth)acrylate, isoheptyl(meth)acrylate, cycloheptyl (meth)acrylate, octyl (meth)acrylate,cyclooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl(meth)acrylate, cyclononyl (meth)acrylate, decyl (meth)acrylate,isodecyl (meth)acrylate, cyclodecyl (meth)acrylate, undecyl(meth)acrylate, isoundecyl (meth)acrylate, cycloundecyl (meth)acrylate,lauryl (meth)acrylate, tridecyl (meth)acrylate, isotridecyl(meth)acrylate, cyclotridecyl (meth)acrylate, tetradecyl (meth)acrylate,isotetradecyl (meth)acrylate, cyclotetradecyl (meth)acrylate, pentadecyl(meth)acrylate), isopentadecyl (meth)acrylate, cyclopentadecyl(meth)acrylate, and combinations thereof. In certain embodiments of thefirst-third embodiments, each functional group F in thepolyfunctionalized diene monomer-containing polymer comprises an epoxideor a thioepoxide. In certain embodiments of the first-third embodiments,each functional group F in the polyfunctionalized dienemonomer-containing polymer comprises an aziridine, which generally canbe considered to be a compound containing the aziridine functional group(a 3-membered heterocyclic group with one amine (—NR—), where R is H,CH₃, and two methylenes (—CH₂—).

In certain embodiments of the first-third embodiments, the chainextender may be chosen based upon compound having a moiety that isreactive with the F functional group of the polyfunctionalized dienemonomer-containing polymer.

In certain embodiments of the first-third embodiments, the chainextender comprises one or more additional functional groups F1 along thebackbone of the polymer. Such functional groups may be chosen based upontheir contribution to desirable properties in the cured polymericmixture, the cured elastomeric 3-dimensional article or final product.As a non-limiting example, the F1 functional groups may be selected tointeract with one or more fillers such as silica filler, i.e., F1comprises a silica-reactive functional group. Thus, in certainembodiments of the first-third embodiments the polyfunctionalized dienemonomer-containing polymer comprises at least one F1 silica-reactivefunctional group along its backbone. Non-limiting examples ofsilica-reactive functional groups include nitrogen-containing functionalgroups, silicon-containing functional groups, oxygen- orsulfur-containing functional groups, and metal-containing functionalgroups. Another specific example of a F1 functional group includesphosphorous-containing functional groups.

Non-limiting examples of nitrogen-containing functional groups that canbe utilized as a F1 silica-reactive functional group along the backboneof the polyfunctionalized diene monomer-containing polymer in certainembodiments include, but are not limited to, any of a substituted orunsubstituted amino group, an amide residue, an isocyanate group, animidazolyl group, an indolyl group, a nitrile group, a pyridyl group,and a ketimine group. The foregoing substituted or unsubstituted aminogroup should be understood to include a primary alkylamine, a secondaryalkylamine, or a cyclic amine, and an amino group derived from asubstituted or unsubstituted imine. In certain embodiments of thefirst-third embodiments, the polyfunctionalized diene monomer-containingpolymer comprises at least one F1 functional group along its backboneselected from the foregoing list of nitrogen-containing functionalgroups.

Non-limiting examples of silicon-containing functional groups that canbe utilized as a F1 silica-reactive functional group along the backboneof the polyfunctionalized diene monomer-containing polymer in certainembodiments include, but are not limited to, an organic silyl or siloxygroup, and more precisely, the functional group may be selected from analkoxysilyl group, an alkylhalosilyl group, a siloxy group, analkylaminosilyl group, and an alkoxyhalosilyl group. Suitablesilicon-containing functional groups for use in functionalizingdiene-based elastomer also include those disclosed in U.S. Pat. No.6,369,167, the entire disclosure of which is herein incorporated byreference. In certain embodiments of the first-third embodiments, thepolyfunctionalized diene monomer-containing polymer comprises at leastone F1 functional group along its backbone selected from the foregoinglist of silicon-containing functional groups.

Non-limiting examples of oxygen- or sulfur-containing functional groupsthat can be utilized as a F1 silica-reactive functional group along thebackbone of the polyfunctionalized diene monomer-containing polymer incertain embodiments include, but are not limited to, a hydroxyl group, acarboxyl group, an epoxy group, a glycidoxy group, a diglycidylaminogroup, a cyclic dithiane-derived functional group, an ester group, analdehyde group, an alkoxy group, a ketone group, a thiocarboxyl group, athioepoxy group, a thioglycidoxy group, a thiodiglycidylamino group, athioester group, a thioaldehyde group, a thioalkoxy group, and athioketone group. In certain embodiments of the first-third embodiments,the foregoing alkoxy group may be an alcohol-derived alkoxy groupderived from a benzophenone. In certain embodiments of the first-thirdembodiments, the polyfunctionalized diene monomer-containing polymercomprises at least one F1 functional group along its backbone selectedfrom the foregoing list of oxygen- or sulfur-containing functionalgroups.

Non-limiting examples of phosphorous-containing functional groups thatcan be utilized as a F1 functional group along the backbone of thepolyfunctionalized diene monomer-containing polymer in certainembodiments include, but are not limited to, organophosphorous compounds(i.e., compounds containing carbon-phosphorous bond(s)) as well asphosphate esters and amides and phosphonates. Non-limiting examples oforganophosphorous compounds include phosphines including alkylphosphines and aryl phosphines. In certain embodiments of thefirst-third embodiments, the polyfunctionalized diene monomer-containingpolymer comprises at least one F1 functional group along its backboneselected from the foregoing list of phosphorous-containing functionalgroups.

Chain Extender

As discussed above, the actinic radiation curable polymeric mixtureoptionally comprises a chain extender based upon F or reactive with F.In other words, in certain embodiments of the first-third embodimentsthe mixture comprises a chain extender, but it is not considered to beessential in all embodiments. Generally, the chain extender is ahydrocarbon or hydrocarbon derivative that is monofunctionalized with afunctional group that reacts with a functional end group of the dienepolymer chain of the polyfunctionalized diene monomer-containing polymerand is used to increase the molecular weight of the polyfunctionalizeddiene monomer-containing polymer (by bonding to one of the F groups ofthe polymer). Preferably, the chain extender lowers the viscosity of theoverall actinic radiation curable polymeric mixture and also acts toincrease the molecular weight of the polyfunctionalized dienemonomer-containing polymer between crosslinks. In certain embodiments ofthe first-third embodiments, the chain extender also increases theelongation at break of the cured elastomeric/polymeric mixture thatresults from actinic radiation curing the polymeric mixture.

In certain embodiments of the first-third embodiments when the chainextender is present, it comprises a compound that is based upon F. Inother words, such a chain extender compound comprises an F group. Incertain embodiments of the first-third embodiments when the chainextender is present, it comprises a compound that is based upon F or acompound that is reactive with F. By reactive with F is meant a compoundcontaining a moiety that will bond with the F group of thepolyfunctionalized diene monomer-containing polymer.

As discussed above, in those embodiments of the first-third embodimentswhere the chain extender is present, it may comprise a hydrocarbon orhydrocarbon derivative with monofunctionality selected from variousfunctional groups either based on F or reactive with F. In certainembodiments of the first-third embodiments when the chain extender ispresent, it is selected so that the Tg of the chain-extendedpolyfunctionalized diene monomer-containing polymer is less than about25° C., including about −65° C. to about 10° C. Preferably, the chainextender is selected so that the Tg of the extended polyfunctionalizeddiene monomer-containing polymer even after crosslinking is less thanabout 25° C., including about −65° C. to about 10° C. In certainembodiments of the first-third embodiments when the chain extender ispresent, it comprises a compound that has a Mw of about 72 to about 1000grams/mole, including about 72 to about 500 grams/mole.

In certain embodiments of the first-third embodiments, when the chainextender is present, it comprises at least one alkyl (meth)acrylatemonomer. In certain such embodiments, the alky (meth)acrylate monomer iscomprised of an alkyl chain selected from C2 to about C18 and having areactive meth(acrylate) head group, termed alkyl functionalized(meth)acrylates; alkyl (meth)acrylate monomers having larger alkylgroups may have a thermal transition, Tm, that is higher than desired.By utilizing as a chain extender a compound/monomer that contains onlyone functional group (e.g., a (meth)acrylate) it is possible to increasethe molecular weight between crosslinks, while reducing the viscosity.

In certain embodiments of the first-third embodiments when the F groupof the polyfunctionalized diene monomer-containing polymer comprises anacrylate or methacrylate, the chain extender comprises at least onealkyl (meth)acrylate monomer. In certain such embodiments, the alky(meth)acrylate monomer is at least one monomer selected from C2 to aboutC18 alkyl functionalized (meth)acrylates; alkyl (meth)acrylate monomershaving larger alkyl groups may have a Tg that is higher than desired andmay unduly increase the Tg of the overall actinic radiation curablepolymeric mixture.

In certain embodiments of the first-third embodiments, the total amountof polyfunctionalized diene monomer-containing polymer and chainextender can be considered to be 100 parts by weight; in certain suchembodiments, the polyfunctionalized diene monomer-containing polymer ispresent in an amount of 1-100 parts by weight and the chain extender ispresent in an amount of 0-99 parts by weight. In other words, the chainextender is optional in certain embodiments. Generally, the relativeamounts of polyfunctionalized diene monomer-containing polymer and chainextender can vary greatly because, as discussed above, upon exposure toactinic radiation the chain extender adds to the polymer and increasesits molecular weight. As a non-limiting example, when the Mn of thepolyfunctionalized diene monomer-containing polymer is relatively low(e.g., about 3,000 grams/mole, polystyrene standard), and the Mw of thechain extender is relatively high (e.g., about 1000 grams/mole), thetotal amount of polyfunctionalized diene monomer-containing polymer andchain extender can comprise relatively less polymer than chain extender.In certain embodiments of the first-third embodiments, thepolyfunctionalized diene monomer-containing polymer is present in anamount of 1-90 parts by weight and the chain extender is present in anamount of 10-99 parts by weight, including 1-80 parts by weightpolyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 20-99 parts by weight, 1-70 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 30-99 parts by weight, 1-60 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 40-99 parts by weight, 1-50 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 50-99 parts by weight, 1-40 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 60-99 parts by weight, 1-30 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 70-99 parts by weight, 1-20 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 80-99 parts by weight, 1-10 parts byweight polyfunctionalized diene monomer-containing polymer and the chainextender is present in an amount of 10-99 parts by weight. In certainembodiments of the first-third embodiments, the polyfunctionalized dienemonomer-containing polymer is present in an amount of 10-99 parts byweight and the chain extender is present in an amount of 1-90 parts byweight, including 20-99 parts by weight polyfunctionalized dienemonomer-containing polymer and the chain extender is present in anamount of 1-80 parts by weight, 30-99 parts by weight polyfunctionalizeddiene monomer-containing polymer and the chain extender is present in anamount of 1-70 parts by weight, 40-99 parts by weight polyfunctionalizeddiene monomer-containing polymer and the chain extender is present in anamount of 1-60 parts by weight, 50-99 parts by weight polyfunctionalizeddiene monomer-containing polymer and the chain extender is present in anamount of 1-50 parts by weight, 60-99 parts by weight polyfunctionalizeddiene monomer-containing polymer and the chain extender is present in anamount of 1-40 parts by weight, 70-99 parts by weight polyfunctionalizeddiene monomer-containing polymer and the chain extender is present in anamount of 1-30 parts by weight, 80-99 parts by weight polyfunctionalizeddiene monomer-containing polymer and the chain extender is present in anamount of 1-20 parts by weight, 90-99 parts by weight polyfunctionalizeddiene monomer-containing polymer and the chain extender is present in anamount of 1-10 parts by weight.

In certain embodiments of the first-third embodiments, when the F groupsof the polyfunctionalized diene monomer-containing polymer comprise(meth)acrylate and the F groups of the chain extender comprise an alkyl(meth)acrylate, the relative amounts of polymer and chain extender areabout 50 parts and 50 parts, respectively, including about 40 to about60 parts polymer and about 60 to about 40 parts chain extender; 40 to 60parts polymer and 60 to 40 parts chain extender; about 45 to about 60parts polymer and about 55 to about 40 parts chain extender; 45 to 60parts polymer and 55 to 40 parts chain extender; about 50 to about 60parts polymer and about 40 to about 50 parts chain extender; 50 to 60parts polymer and 40 to 50 parts chain extender; about 55 to about 60parts polymer and about 40 to about 45 parts chain extender; and 55 to60 parts polymer and 40 to 45 parts chain extender.

In certain embodiments of the first-third embodiments, in addition tobeing monofunctionalized with at least one F group or a functional groupreactive with F, the chain extender is further functionalized with atleast one functional group F2 that is molecular oxygen reactive.Non-limiting examples of suitable F2 groups include various amines,including, but not limited to, tertiary amines, secondary amines, andprimary amines; thiols; silanes; phosphites, tin-containing compounds,lead containing compounds, and germanium-containing compounds.Incorporating at least one molecular oxygen reactive F2 functional groupinto the chain extender reduces the amount of undesirable oxidation thatmay otherwise occur from either solubilized oxygen within the actinicradiation curable polymeric mixture or atmospheric oxygen. Without beingbound by theory, a functional group F2 that is molecular oxygen reactivecan react with any peroxy radicals that are generated (e.g., from thereaction of a free radical with molecular oxygen) to create a newinitiator by hydrogen absorption; this reaction avoid or minimizes theundesirable reaction between a peroxy radical and an initiator (whichwill yield a non-productive product and consume the initiator). Theamount of F2 functionalization on the chain extender may vary. Incertain embodiments of the first-third embodiments, the chain extenderis about 10 to 100% functionalized with at least one functional group F2that is molecular oxygen reactive, including 10 to 100% functionalized,about 20 to 100% functionalized, 20 to 100% functionalized, about 30 to100% functionalized, 30 to 100% functionalized, about 40 to 100%functionalized, 40 to 100% functionalized, about 50 to 100%functionalized, 50 to 100% functionalized, about 10 to about 90%functionalized, 10 to 90% functionalized, about 10 to about 80%functionalized, 10 to 80% functionalized, about 10 to about 70%functionalized, 10 to 70% functionalized, about 10 to about 60%functionalized, 10 to 60% functionalized, about 10 to about 50%functionalized, and 10 to 50% functionalized. In other embodiments, inaddition to comprising at least one functional group F2 that ismolecular oxygen reactive or as an alternative to comprising at leastone functional group F2 that is molecular oxygen reactive, a separatemolecular oxygen reactive ingredient can be utilized in the actinicradiation curable polymeric mixture. Generally, this separate ingredientcomprises a hydrocarbon or hydrocarbon derivative functionalized with atleast one of the functional groups discussed above for F2.

Photoinitiator

As discussed above, the actinic radiation curable polymeric mixturecomprises at least one actinic radiation sensitive photoinitiator. Incertain embodiments of the first-third embodiments, the polymericmixture comprises two, three, or more one actinic radiation sensitivephotoinitiators. Generally, the purpose of the photoinitiator is toabsorb actinic radiation (light) and generate free radicals or a Lewisacid that will react with the functional groups of the polymer resultingin polymerization. Two types of actinic radiation sensitivephotoinitiators exist: free radical and cationic. Free radicalphotoinitiators can themselves be separated into two categories, thosethat undergo cleavage upon irradiation to generate two free radicals(e.g., benzoins, benzoin ethers, and alpha-hydroxy ketones) and thosethat form an excited state upon irradiation and then abstract an atom orelectron from a donor molecule which itself then acts as the initiatingspecies for polymerization (e.g., benzophenones). In certain embodimentsof the first-third embodiments disclosed herein, the photoinitiatorcomprises at least one free radical photoinitiator. In certainembodiments of the first-third embodiments disclosed herein, thephotoinitiator comprises at least one cationic photoinitiator. Incertain embodiments of the first-third embodiments disclosed herein, thephotoinitiator comprises a combination of at least one free radicalphotoinitiator and at least one cationic photoinitiator.

When a photoinitiator is utilized, various photoinitiators are suitablefor use in the actinic radiation curable polymeric mixtures. In certainembodiments of the first-third embodiments disclosed herein, thephotoinitiator comprises at least one of: a benzoin, an aryl ketone, analpha-amino ketone, a mono- or bis(acyl)phosphine oxide, a benzoin alkylether, a benzil ketal, a phenylglyoxalic ester or derivatives thereof,an oxime ester, a per-ester, a ketosulfone, a phenylglyoxylate, aborate, and a metallocene. In certain embodiments of the first-thirdembodiments disclosed herein, the photoinitiator comprises at least oneof: a benzophenone, an aromatic α-hydroxyketone, a benzilketal, anaromatic α-aminoketone, a phenylglyoxalic acid ester, amono-acylphosphinoxide, a bis-acylphosphinoxide, and atris-acylphosphinoxide. In certain embodiments of the first-thirdembodiments disclosed herein, the photoinitiator is selected frombenzophenone, benzildimethylketal, 1-hydroxy-cyclohexyl-phenyl-ketone,1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one,2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one,(4-methylthiobenzoyl)-1-methyl-1-morpholinoethane,(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane,(4-morpholinobenzoyl)-1-(4-methylbenzyl)-1-dimethylaminopropane,(2,4,6-trimethylbenzoyl)diphenylphosphine oxide,bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl)phosphine oxide,bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3,3-trimethyl-indan-5-yl}-2-methyl-propan-1-one,1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzyloxime),oligo[2-hydroxy-2-methyl-1-[4-methylvinyl]phenyl]propanone,2-hydroxy-2-methyl-1-phenyl propan-1-one, and combinations thereof.

The amount of actinic radiation sensitive photoinitiator(s) utilized canvary. In certain embodiments of the first-third embodiments disclosedherein, when the photoinitiator is present, the actinic radiationcurable polymeric mixture comprises about 1 to about 10 parts by weightof the photoinitiator, including about 2 to about 5 parts by weight (allamounts based upon 100 total parts of polyfunctionalized dienemonomer-containing polymer and chain extender). The foregoing amountsshould be understood to apply to both free radical and cationicphotoinitiators and to refer to the total amounts (by weight) of allphotoinitiators used in the actinic radiation curable polymeric mixture.

Photosensitizer

As discussed above, in certain embodiments of the first-thirdembodiments, the actinic radiation curable polymeric mixture comprises aphotosensitizer. In other words, in certain embodiments of thefirst-third embodiments, the photosensitizer is optional. Generally, the“photosensitizer” is a light absorbing compound used to enhance thereaction of a photoinitiator; it may absorb part of the actinicradiation (light) that the photoinitiator cannot absorb and transfer theenergy to the photoinitiator. Upon photoexcitation, a photosensitizerleads to energy or electron transfer to a photoinitiator.

In those embodiments of the first-third embodiments where aphotosensitizer is used, the amount of photosensitizer utilized canvary. (As discussed above, the photosensitizer is not necessarilypresent in every embodiment disclosed herein.) In certain embodiments ofthe first-third embodiments disclosed herein, when the photosensitizeris present, the actinic radiation curable polymeric mixture comprisesabout 0.1 to about 5 parts by weight of the photosensitizer, includingabout 0.1 to about 2 parts by weight (all amounts based upon 100 totalparts of polyfunctionalized diene monomer-containing polymer and chainextender).

When a photosensitizer is utilized, various photosensitizers aresuitable for use in the actinic radiation curable polymeric mixtures. Incertain embodiments of the first-third embodiments disclosed herein, thephotosensitizer comprises at least one of a ketocoumarin, a xanthone, athioxanthone, a polycyclic aromatic hydrocarbon, and an oximesterderived from aromatic ketone. Exemplary ketocoumarins are disclosed inTetrahedron 38, 1203 (1982), and U.K. Patent Publication 2,083,832(Specht et al.).

Crosslinker

As discussed above, the actinic radiation curable mixture comprises apolyfunctional crosslinker reactive with the functional group F of thepolyfunctionalized diene monomer-containing polymer. Generally, thepolyfunctional crosslinker functions to increase the amount ofcrosslinking within each diene polymer chain of the polyfunctionalizeddiene monomer-containing polymer, between (separate) diene polymerchains of polyfunctionalized diene monomer-containing polymers, or both,thereby forming a network. Generally, an increased amount of crosslinkeror crosslinking will lower the Mc of the crosslinked (cured)polyfunctionalized diene monomer-containing polymer, thereby resultingin a higher modulus and a lower Eb. In certain embodiments of thefirst-third embodiments, the polyfunctional crosslinker is a hydrocarbonor hydrocarbon derivative polyfunctionalized with a functional group F.In other words, such a crosslinker comprises multiple F groups. Incertain embodiments of the first-third embodiments, the crosslinker is ahydrocarbon or hydrocarbon derivative polyfunctionalized with afunctional group F or a functional group that is reactive with F. Byreactive is meant a moiety that will bond with at least two F groups ofthe polyfunctionalized diene monomer-containing polymer.

Generally, the crosslinker is a polyfunctionalized hydrocarbon orhydrocarbon derivative containing at least two functional groupsreactive with F. In certain embodiments of the first-third embodiments,the crosslinker is di-functional and in other embodiments, thecrosslinker is tri-functional, tetra-functional, or furtherfunctionalized. While the crosslinker is based upon a hydrocarbon orhydrocarbon derivative, it should be understood that it can also bepolymer-like in that it can comprise either a single base unit ormultiple, repeating base units.

Various compounds are suitable for use as the crosslinker. In certainembodiments of the first-third embodiments, the crosslinker contains atleast two (meth)acrylate functional groups. In certain embodiments ofthe first-third embodiments, the crosslinker comprises a polyol(meth)acrylate prepared from an aliphatic diol, triol, or tetraolcontaining 2-100 carbon atoms; in such embodiments, the functional groupof the crosslinker is (meth)acrylate. Various crosslinkers comprising atleast two (meth)acrylate groups are commercially available. In certainembodiments of the first-third embodiments, the crosslinker comprises atleast one of the following: Trimethylolpropane tri(meth)acrylate,Pentaerythritol tetraacrylate, Pentaerythritol triacrylate,Trimethylolpropane ethoxylate triacrylate, Acrylated epoxidized soybeanoil, Ditrimethylol Propane Tetraacrylate, Di-pentaerythritolPolyacrylate, Di-pentaerythritol Polymethacrylate, Di-pentaerythritoltriacrylate, Di-pentaerythritol trimethacrylate, Di-pentaerythritoltetracrylate, Di-pentaerythritol tetramethacrylate, Di-pentaerythritolpent(meth)acrylate, Di-pentaerythritol hexa(meth)acrylate,Pentaerythritol Poly(meth)acrylate, Pentaerythritol tri(meth)acrylate,Pentaerythritol tetra(meth)acrylate, Pentaerythritolpenta(meth)acrylate, Pentaerythritol hexa(meth)acrylate, Ethoxylatedglycerine triacrylate, ε-Caprolactone ethoxylated isocyanuric acidtriacrylate and Ethoxylated isocyanuric acid triacrylate,Tris(2-acryloxyethyl) Isocyanulate, Propoxylated glyceryl Triacrylate,ethyleneglycol diacrylate, 1,6-hexanediol diacrylate, neopentylglycoldi(meth)acrylate, ethyleneglycol dimethacrylate (EDMA),polyethyleneglycol di(meth)acrylates, polypropyleneglycoldi(meth)acrylates, polybutyleneglycol di(meth)acrylates,2,2-bis(4-(meth)acryloxyethoxyphenyl) propane,2,2-bis(4-(meth)acryloxydiethoxyphenyl) propane, di(trimethylolpropane)tetra(meth)acrylate, and combinations thereof.

In certain embodiments of the first-third embodiments, the crosslinkercomprises a polyallylic compound prepared from an aliphatic diol, triolor tetraol containing 2-100 carbon atoms. Exemplary polyallyliccompounds useful as crosslinker include those compounds comprising twoor more allylic groups, non-limiting examples of which includetriallylisocyanurate (TAIC), triallylcyanurate (TAC), and the like, andcombinations thereof.

In certain embodiments of the first-third embodiments, the crosslinkercomprises epoxy functional groups, aziridine functional groups, vinylfunctional groups, allyl functional groups, or combinations thereof.

In certain embodiments of the first-third embodiments, the crosslinkercomprises a polyfunctional amine with at least two amine groups permolecule. In certain such embodiments, the polyfunctional amine is analiphatic amine. Exemplary polyfunctional amines include, but are notlimited to, diethylene triamine, ethylene diamine, triethylenetetramine, tetraethylene pentamine, hexamethylerie diamine,1,2-diaminocyclohexane, amino ethyl piperazine, and the like, andcombinations thereof.

In certain embodiments of the first-third embodiments, thepolyfunctional crosslinker comprises a combination of two types offunctional groups, i.e., a functional group capable of crosslinking atleast two diene polymer chains based upon cationic radiation and afunctional group capable of crosslinking at least two diene polymerchains based upon free radical radiation. The combination of two typesof functional groups may be present on the same polyfunctionalcrosslinker or on separate crosslinkers (i.e., each with one type offunctional group). In certain embodiments of the first-thirdembodiments, the polyfunctional crosslinker comprises a combination ofat least one functional group selected from acrylate groups,methacrylate groups, polyallylic groups, and polyfunctional amines withat least one functional group selected from epoxy groups, aziridinegroups, vinyl groups, and allyl groups.

Filler(s)

In certain embodiments of the first-third embodiments, the actinicradiation curable polymeric mixture further comprises at least onefiller; in certain such embodiments, the at least one filler comprises areinforcing filler, preferably a non-carbon black reinforcing filler(i.e., a reinforcing filler other than carbon black). In certainembodiments of the first-third embodiments, when at least one filler isutilized it comprises a non-carbon black filler (i.e., no carbon blackfiller is included in the at least one filler). As used herein, the term“reinforcing filler” is used to refer to a particulate material that hasa nitrogen absorption specific surface area (N₂SA) of more than about100 m²/g, and in certain instances more than 100 m²/g, more than about125 m²/g, more than 125 m²/g, or even more than about 150 m²/g or morethan 150 m²/g. Alternatively or additionally, the term “reinforcingfiller” can also be used to refer to a particulate material that has aparticle size of about 10 nm to about 50 nm (including 10 nm to 50 nm).In certain embodiments of the first-third embodiments, the at least onefiller comprises a non-carbon black reinforcing filler having a surfacearea of more than 150 m²/g, more than 200 m²/g, more than 250 m²/g, morethan 300 m²/g, more than 350 m²/g, more than 400 m²/g, 150-400 m²/g,150-350 m²/g, 200-400 m²/g, or 200-350 m²/g. In certain embodiments ofthe first-third embodiments, the actinic radiation curable polymericmixture further comprises at least one metal or metal oxide filler. Inother words, the mixture further comprises at least one metal filler, atleast one metal oxide filler, or combinations thereof. Various metalfillers and metal oxide fillers are suitable for use in variousembodiments of the actinic radiation curable polymeric mixture. Incertain embodiments of the first-third embodiments, the at least onemetal or metal oxide filler comprises at least one of: silica (in itsvarious forms only some of which are listed below), aluminum hydroxide,starch, talc, clay, alumina (Al₂O₃), aluminum hydrate (Al₂O₃H₂O),aluminum hydroxide (Al(OH)₃), aluminum carbonate (Al₂(CO₃)₂), aluminumnitride, aluminum magnesium oxide (MgOAl₂O₃), aluminum silicate(Al₂SiO₅, Al₄.3SiO₄.5H₂O etc.), aluminum calcium silicate(Al₂O₃.CaO₂SiO₂, etc.), pyrofilite (Al₂O₃4 SiO₂.H₂O), bentonite(Al₂O₃.4SiO₂.2H₂O), boron nitride, mica, kaolin, glass balloon, glassbeads, calcium oxide (CaO), calcium hydroxide (Ca(OH)₂), calciumcarbonate (CaCO₃), magnesium carbonate, magnesium hydroxide (MH(OH)₂),magnesium oxide (MgO), magnesium carbonate (MgCO₃), magnesium silicate(Mg₂SiO₄, MgSiO₃ etc.), magnesium calcium silicate (CaMgSiO₄), titaniumoxide, titanium dioxide, potassium titanate, barium sulfate, zirconiumoxide (ZrO₂), zirconium hydroxide [Zr(OH)₂.nH₂O], zirconium carbonate[Zr(CO₃)₂], crystalline aluminosilicates, zinc oxide (i.e., reinforcingor non-reinforcing), and combinations thereof. graphite, clay, titaniumdioxide, magnesium dioxide, aluminum oxide (Al₂O₃), silicon nitride,calcium silicate (Ca₂SiO₄, etc.), crystalline aluminosilicates, siliconcarbide, single walled carbon nanotubes, double walled carbon nanotubes,multi walled carbon nanotubes, grapheme oxide, graphene, silver, gold,platinum, copper, strontium titanate (StTiO₃), barium titanate (BaTiO₃),silicon (Si), hafnium dioxide (HfO₂), manganese dioxide (MnO₂), ironoxide (Fe₂O₄ or Fe₃O₄), cerium dioxide (CeO₂), copper oxide (CuO),indium oxide (In₂O₃), indium tin oxide (In₂O₃ SnO₂). In certainembodiments of the first-third embodiments, the at least one fillercomprises at least one of: silica (in its various forms only some ofwhich are listed below), aluminum hydroxide, starch, talc, clay, alumina(Al₂O₃), aluminum hydrate (Al₂O₃H₂O), aluminum hydroxide (Al(OH)₃),aluminum carbonate (Al₂(CO₃)₂), aluminum nitride, aluminum magnesiumoxide (MgOAl₂O₃), aluminum silicate (Al₂SiO₅, Al₄.3SiO₄.5H₂O etc.),aluminum calcium silicate (Al₂O₃.CaO₂SiO₂, etc.), pyrofilite (Al₂O₃4SiO₂.H₂O), bentonite (Al₂O₃.4SiO₂.2H₂O), boron nitride, mica, kaolin,glass balloon, glass beads, calcium oxide (CaO), calcium hydroxide(Ca(OH)₂), calcium carbonate (CaCO₃), magnesium carbonate, magnesiumhydroxide (MH(OH)₂), magnesium oxide (MgO), magnesium carbonate (MgCO₃),magnesium silicate (Mg₂SiO₄, MgSiO₃ etc.), magnesium calcium silicate(CaMgSiO₄), titanium oxide, titanium dioxide, potassium titanate, bariumsulfate, zirconium oxide (ZrO₂), zirconium hydroxide [Zr(OH)₂.nH₂O],zirconium carbonate [Zr(CO₃)₂], crystalline aluminosilicates, zinc oxide(i.e., reinforcing or non-reinforcing), and combinations thereof.graphite, clay, titanium dioxide, magnesium dioxide, aluminum oxide(Al₂O₃), silicon nitride, calcium silicate (Ca₂SiO₄, etc.), crystallinealuminosilicates, silicon carbide, single walled carbon nanotubes,double walled carbon nanotubes, multi walled carbon nanotubes, graphemeoxide, graphene, silver, gold, platinum, copper, strontium titanate(StTiO₃), barium titanate (BaTiO₃), silicon (Si), hafnium dioxide(HfO₂), manganese dioxide (MnO₂), iron oxide (Fe₂O₄ or Fe₃O₄), ceriumdioxide (CeO₂), copper oxide (CuO), indium oxide (In₂O₃), indium tinoxide (In₂O₃SnO₂).

In certain embodiments of the first-third embodiments, the at least onefiller includes ground, cured rubber, optionally in combination with oneof more of the foregoing fillers. As used herein, the term “ground,cured rubber” refers to cured, i.e., vulcanized (crosslinked) rubberthat has been ground or pulverized into particulate matter; variousparticle size ground, cured rubber may be utilized. In certainembodiments of the first-third embodiments where ground, cured rubber isutilized, it has an average particle size in the range of about 50 μm toabout 250 μm (including 50 μm to 250 μm), preferably an average particlesize of about 74 μm to about 105 μm (including 74 μm to 105 μm. Theaverage particle size of ground, cured rubber particles may be measuredby any conventional means known in the art including the methodsaccording to ASTM D5644. Examples of suitable sources of rubber for theground, cured rubber include used tires. It is well known to thoseskilled in the art that tires are prepared from natural and syntheticrubbers that are generally compounded using fillers including carbonblack and sometimes also including silica. The source of the ground,cured rubber used in accordance with the first, second, and thirdembodiments disclosed herein may vary, but in certain embodiments can betires (or rubber from such tires) produced with a carbon black filler,with a silica filler, or with mixtures of both. Exemplary sourcesinclude tires from passenger cars, light trucks, or combinations ofboth. In certain embodiments of the first-third embodiments whereground, cured rubber is utilized, the ground, cured rubber is free ofcarbon black filler (i.e., the ground, cured rubber contains less than 1phr carbon black filler or even 0 phr carbon black filler).

When at least one filler is utilized in the actinic radiation curablepolymeric mixture, the total amount utilized may vary widely. Generally,the total amount of filler utilized will vary depending upon the type offiller and the properties sought in the cured polymeric mixture producedfrom the actinic radiation curable polymeric mixture. As well, incertain embodiments of the first-third embodiments, the amount of fillerwill also be adjusted based upon any viscosity increase that it causesto the overall actinic radiation curable polymeric mixture. In certainembodiments of the first-third embodiments, the total amount of fillerutilized in the actinic radiation curable polymeric mixture is an amountthat does not cause the viscosity of the mixture to exceed about 10,000cps (at 25° C.), preferably not exceeding about 5,000 cps (at 25° C.).In certain embodiments of the first-third embodiments disclosed herein,the at least one filler is present in a total amount (i.e, the total ofamount of all fillers if more than one is present) of up to about ⅔ ofthe total volume (e.g., 67%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%,25%, 20%, 15%, 10%, 5%, 2%, or 1%) of the actinic radiation curablepolymeric mixture. In certain embodiments of the first-third embodimentsdisclosed herein, the at least one filler is present in a total amount(i.e, the total of amount of all fillers if more than one is present) ofabout 40 to about 80 parts (based upon 100 total parts of (a) and (b)).In certain embodiments of the first-third embodiments disclosed herein,the only fillers utilized are non-carbon black fillers and the totalamount of all non-carbon black fillers (i.e, the total of amount of allnon-carbon black fillers if more than one is present) is of up to about⅔ of the total volume (e.g., 67%, 65%, 60%, 55%, 50%, 45%, 40%, 35%,30%, 25%, 20%, 15%, 10%, 5%, 2%, or 1%) of the actinic radiation curablepolymeric mixture. In certain embodiments of the first-third embodimentsdisclosed herein, the only fillers utilized are non-carbon black fillersand the total amount of all non-carbon black fillers (i.e, the total ofamount of all non-carbon black fillers if more than one is present) isabout 40 to about 80 parts (based upon 100 total parts of (a) and (b)).

In certain embodiments of the first-third embodiments, at least onecarbon black filler is utilized; in such embodiments the at least onecarbon black filler may be utilized as the only filler but mayalternatively be utilized in combination with one or more non-carbonblack filler such as those discussed above. In those embodiments of thefirst-third embodiments disclosed herein that include at least onecarbon black filler, the total amount of carbon black filler can varyand may include amounts such as at least 0.01 parts, 0.01 to less than 1part, 0.05 to 0.5 parts (based upon 100 total parts of (a) and (b)).

In those embodiments of the first-third embodiments where at least onecarbon black is utilized as a filler, various carbon blacks can beutilized. In certain embodiments of the first-third embodiments, one ormore reinforcing carbon blacks are utilized. In other embodiments of thefirst-third embodiments, one or more non-reinforcing carbon blacks areutilized. In yet other embodiments of the first-third embodiments, atleast one reinforcing carbon black is used in combination with at leastone non-reinforcing carbon black. Carbon blacks having a nitrogensurface area of greater than 30 m²/g and a DBP absorption of greaterthan 60 cm³/100 g) are referred to herein as “reinforcing carbon blacks”and carbon blacks having a lower nitrogen surface area and/or lower DBPabsorption are referred to herein as “non-reinforcing carbon blacks.”The nitrogen surface area and the DBP absorption provide respectivecharacterizations of the particle size and structure of the carbonblack. The nitrogen surface area is a conventional way of measuring thesurface area of carbon black. Specifically, the nitrogen surface area isa measurement of the amount of nitrogen which can be absorbed into agiven mass of carbon black. Preferably, the nitrogen surface area forcarbon black fillers is determined according to ASTM test D6556 orD3037. The DBP absorption is a measure of the relative structure ofcarbon black determined by the amount of DBP a given mass of carbonblack can absorb before reaching a specified viscous paste. Preferably,the DBP absorption for carbon black fillers is determined according toASTM test D2414. Among the useful carbon blacks are furnace black,channel blacks, and lamp blacks. More specifically, examples of usefulcarbon blacks include super abrasion furnace (SAF) blacks, high abrasionfurnace (HAF) blacks, fast extrusion furnace (FEF) blacks, fine furnace(FF) blacks, intermediate super abrasion furnace (ISAF) blacks,semi-reinforcing furnace (SRF) blacks, medium processing channel blacks,hard processing channel blacks and conducting channel blacks. Exemplaryreinforcing carbon blacks include: N-110, N-220, N-339, N-330, N-351,N-550, and N-660, and combinations thereof. Exemplary non-reinforcingcarbon blacks include: thermal blacks or the N9 series carbon blacks(also referred to as the N-900 series), such as those with the ASTMdesignation N-907, N-908, N-990, and N-991.

Processes for Producing a Cured Polymeric Product

As discussed above, the third embodiment disclosed herein is directed toa process for producing a cured polymeric product. The processcomprises: providing an additive manufacturing device comprising asource of actinic radiation, an exterior support structure having anatmosphere inside, an interior tank capable of containing a liquidmixture and having an atmosphere above the tank, and an interior supportstructure; providing to the interior tank a liquid actinic radiationcurable polymeric mixture comprising: (i) a polyfunctionalized dienemonomer-containing polymer having the formula: [P][F]_(n) where Prepresents a diene polymer chain, F represents a functional group, n is2 to about 15, and each F can be the same or different; (ii) optionallya chain extender based upon F or reactive with F; (iii) at least oneactinic radiation sensitive photoinitiator; (iv) optionally, aphotosensitizer; and (v) a polyfunctional crosslinker reactive with F;repeatedly forming upon the interior support structure a layer from theliquid mixture; using actinic radiation to cure each layer, therebyproducing a cured polymeric product. According to the third embodiment,at least one of the following has an oxygen level of less than 50 ppm(e.g., 49 ppm, 45 ppm, 40 ppm, 35 ppm, 30 ppm, 25 ppm, 20 ppm, 15 ppm,10 ppm, 5 ppm, 1 ppm, or less), including: the liquid actinic radiationcurable polymeric mixture within the interior tank, the atmosphere abovethe liquid actinic radiation curable polymeric mixture within theinterior tank, the atmosphere surrounding the interior supportstructure, or the atmosphere inside the exterior support structure; incertain such embodiments, the oxygen level of at least one of theforegoing has an oxygen level of less than 40 ppm, less than 30 ppm,less than 20 ppm, or less than 10 ppm. In certain embodiments of thethird embodiment, an additive manufacturing cartridge according to thefirst embodiment disclosed herein is utilized in the process. Theprocesses of the third embodiment should be understood to include theuse of an additive manufacturing cartridge according to the firstembodiment (including all of the variations thereto, as described above,as if fully set forth herein). In certain embodiments of the thirdembodiment, the liquid actinic radiation curable polymeric mixture isprovided in a cartridge having an oxygen impermeable layer surroundingthe liquid actinic radiation curable polymeric mixture.

In certain embodiments of the third embodiment, the process furthercomprises adding an inert gas to at least one of: (a) the atmosphereabove the liquid actinic radiation curable polymeric mixture within theinterior tank of the additive manufacturing device; (b) the atmospheresurrounding the interior support structure of the additive manufacturingdevice; or (c) the atmosphere inside the exterior support structure.Various inert gases such as nitrogen, argon, helium, carbon dioxide, andcombinations thereof may be utilized in various embodiments of theprocesses of the third embodiment. In certain embodiments of the thirdembodiment the inert gas comprises nitrogen. In certain embodiments ofthe third embodiment, the process further comprises continuous additionof an inert gas to at least one of (a), (b), or (c), as discussed above,during the process of repeatedly forming layers from the liquid mixtureand until a cured polymeric product has been produced. In certainembodiments of the third embodiment wherein the process includes the useof a cartridge (i.e., an actinic radiation manufacturing cartridge), theprocess further comprises adding an inert gas (e.g, as discussed above)to the cartridge to facilitate providing of the liquid actinic radiationcurable polymeric mixture to the interior tank. In certain embodimentsof the third embodiment wherein the process includes the use of acartridge (i.e., an actinic radiation manufacturing cartridge), theprocess further comprises removing gas from the cartridge (e.g., gasthat may have been intentionally included with the contents of thecartridge and/or gas that may have entered the cartridge during storageor shipping) and supplying inert gas to the cartridge as the liquidactinic radiation curable polymeric mixture is removed during forming.

In certain embodiments of the third embodiment, the cartridge utilizedin the process comprises at least two separate compartments, asdiscussed in more detail above.

As discussed above, the third embodiment disclosed herein is directed toa process for producing a cured polymeric product. This processcomprises providing an additive manufacturing device comprising a sourceof actinic radiation, an exterior support structure, an interior tankcapable of containing a liquid mixture, and an interior supportstructure; providing a liquid mixture comprising an actinic radiationcurable polymeric mixture according to the first embodiments disclosedherein (i.e., as previously described) to the interior tank; repeatedlyforming upon a support structure a layer from the liquid mixture; usingactinic radiation to cure each layer; thereby producing a curedpolymeric product. According to the third embodiment disclosed herein,various types of additive manufacturing devices may be utilized.Generally, a great variety of additive manufactures devices arecommercially available from companies including, but not limited to, 3DSystems, Inc. (Rock Hill, S.C.) and Stratasys Ltd. (Eden Prairie,Minn.). In certain embodiments, the additive manufacturing device formsthe product by a process that comprises solidifying each layer by usingthe actinic radiation to trace a pattern in the liquid material; incertain such embodiments the device contains no printer head; in certainsuch embodiments, such a process can be referred to as vatphotopolymerization. In certain embodiments of the third embodiment, theadditive manufacturing device forms the product by a process thatcomprises solidifying each layer by using actinic radiation to provideat least one pattern on the liquid material, such a process can bereferred to as laser rastering. In certain embodiments of the thirdembodiment, the laser rastering can be understood as involving the useof pinpoint radiation which is moved across the service to result in anoverall pattern being provided. In certain embodiments of the thirdembodiment, the additive manufacturing device forms the product by aprocess that comprises solidifying each layer by using actinic radiationto project at least one image on the liquid material, such a process canbe referred to as digital light processing. As used herein, the phrasetracing a pattern in the liquid material is intended to encompass bothdigital light processing and laser rastering processes. In otherembodiments, the additive manufacturing device forms the product bydispensing the mixture from a printing head having a set of nozzles; incertain such embodiments, such a process can be referred to as materialjetting.

According to the process of the third embodiment, the thickness of eachlayer that is formed by the additive manufacturing device (e.g., uponthe support structure) may vary. In certain embodiments, each layer hasa thickness of about 0.01 mm to about 1 mm, including a thickness of0.01 mm to 1 mm, about 0.1 mm to about 0.3 mm, and 0.1 mm to 0.3 mm.According to the third embodiment, the materials of construction for thesupport structure of the additive manufacturing device upon which theproduct is formed may vary. In certain embodiments of the thirdembodiment, the support structure comprises polysiloxane polymer (e.g.,polydimethylsiloxane or PDMS), a halogenated polymer coating, ahalogenated wax coating, or a combination thereof. Non-limiting examplesof halogenated polymer coatings include fluorinated halogenated polymerssuch as polytetrafluoroethylene (PTFE, sold under the tradename Teflon®by DuPont). Non-limiting examples of halogenated wax coatings includefluorinated waxes, chlorinated waxes, brominated waxes, and combinationsthereof. Various commercial sources for halogenated waxes exist such asDover Chemical Corporation (Dover, Ohio) which sells Doverguard® brandbrominated waxes and Chlorez® brand chlorinated waxes. Use of theforegoing materials of construction for the support structure oremploying those materials as a coating for the support structure uponwhich the product is formed can facilitate the processes of the thirdembodiment and production of the resulting products by enabling theproduct to be more easily removed from the support structure, preferablywithout curing or otherwise sticking to the support structure such thatremoval therefrom involves tearing or breaking one or more layers of theproduct. As those of skill in the art will appreciate, the particularmaterial of construction used for the support structure may beintentionally varied depending upon the ingredients contained in theactinic radiation curable polymeric mixture (in particular, the type ofchain extender utilized).

The wavelength of the actinic radiation used in the processes of thethird embodiment disclosed herein may vary, depending upon theparticular type of additive manufacturing device chosen or the settingchosen for a particular additive manufacturing devices (some devicesallow the user to select different wavelength ranges). In certainembodiments, the actinic radiation has a wavelength in the UV to Visiblerange. In certain embodiments, the actinic radiation (light) has awavelength of about 320 to less than 500 nm, including about 350 toabout 450 nm, and about 365 to about 405 nm.

In certain embodiments of the processes of the third embodimentdisclosed herein, the process includes the use of a cartridge to providethe liquid mixture comprising the actinic radiation curable polymericmixture. In certain embodiments of the processes of the third embodimentdisclosed herein, the interior tank of the additive manufacturing devicefurther comprises a component capable of receiving a liquid mixture fromat least one cartridge. In other words, in such embodiments, theinterior tank of the additive manufacturing device is capable ofreceiving a liquid mixture from at least one cartridge.

Various combinations of one or more cartridges to contain theingredients of the actinic radiation curable polymeric mixture in itsvarious sub-embodiments (as described above) are envisioned for use incertain embodiments of the processes of the third embodiment. In certainembodiments of the third embodiment, the process comprises the use of atleast two cartridges, with one cartridge comprising: thepolyfunctionalized diene monomer-containing polymer having the formula[P][F]_(n) where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent and chain extender based upon F or reactive with F and thesecond cartridge comprising chain extender based upon F or reactive withF along with at least one of an actinic radiation sensitivephotoinitiator and a photosensitizer. In certain of the foregoingembodiments, the second cartridge further comprises a crosslinkerreactive with F; alternatively, a third cartridge comprising acrosslinker reactive with F can be provided.

Cured Elastomeric/Polymeric Product or Article

As discussed above, the third embodiment disclosed herein is directed toa process for producing a cured polymeric product. Additionally, thecartridges of the first embodiment (and the cartridges made using theprocess of the second embodiment) can be used to produce a curedpolymeric product. In certain embodiments of the first-thirdembodiments, the cured polymeric product comprises a crosslinkedpolyfunctionalized diene polymer comprising a diene polymer chainbackbone [P], multiple functional groups F where each F is the same ordifferent, and crosslinkages between pairs of functional groups. Inother embodiments of the first-third embodiments, the cured polymericproduct can be understood as comprising a cured version of the actinicradiation curable polymeric mixture as previously described.

In certain embodiments of the first-third embodiments, the curedpolymeric product comprises an elastomeric polymeric product. In certainembodiments of the first-third embodiments, the cured polymeric productis elastomeric. As used herein, the term elastomeric can be understoodaccording to the following explanation. Yield as used herein refers tothe onset of plastic deformation in a material under an applied load.Plastic deformation is deformation that remains after the load isremoved. The yield point is the peak in a load-elongation curve (load ony axis, elongation on x axis) at which plastic flow becomes dominant.Thus, as used herein, the term elastomer or elastomeric refers to amaterial which does not exhibit any definite yield point or area ofplastic deformation; in other words, the deformation of an elastomericmaterial remains elastic as opposed to becoming plastic.

In certain embodiments of the first-third embodiments, the curedelastomeric product comprises crosslinkages which contain no sulfur. Incertain embodiments of the first-third embodiments, the curedelastomeric product comprises crosslinkages which are essentially freeof sulfur. By essentially free of sulfur is meant that no more thanabout 1 ppm of sulfur in the overall actinic radiation curable polymericmixture of the cured polymeric product, including less than 1 ppm, lessthan about 0.1 ppm, less than 0.1 ppm, and 0 ppm. In certain embodimentsof the first-third embodiments, the cured elastomer mixture comprisescrosslinkages which contain sulfur, various amounts of which arepossible.

Kits

In certain embodiments of the first embodiment, one or more cartridgescan be assembled into a kit (i.e., such a kit comprises at least twocontainers or cartridges as previously described). Such kits can beuseful in producing a cured polymeric product by additive printing. Forexample, by the use of such kits, a manufacturer may utilize differenttypes and combinations of polyfunctionalized diene monomer-containingpolymer(s), chain extender(s), photoinitiator(s), photosensitizer(s),and crosslinker(s). The use of a kit with multiple cartridges or couldprovide an advantage in material jetting processes where the machine andprint head could be used to selectively dispense the materials fromdifferent cartridges or containers without the need to pre-mix thematerials. Use of a kit comprising at least one cartridge or containerwith at least one filler would allow for the filler to be in a stabledispersion and mixed (as needed) with the other components either justprior to or upon printing. In certain embodiments, the kit comprises atleast two cartridges (or a cartridge with at least two compartments),wherein at least one cartridge (or compartment) comprises apolyfunctionalized diene monomer-containing polymer having the formula[P][F]_(n) where P represents a diene polymer chain, F represents afunctional group, n is 2 to about 15, and each F can be the same ordifferent and a chain extender based upon F or compatible with F; and atleast a second cartridge (or compartment) comprises a chain extenderbased upon F or compatible with F, at least one of an actinic radiationsensitive photoinitiator and a photosensitizer, and optionally acrosslinker reactive with F. In certain of the foregoing embodiments ofthe kit, at least one cartridge (or compartment) further comprises atleast one metal or metal oxide filler. In certain of the foregoingembodiments of the kit, at least cartridge (or compartment) furthercomprises at least one filler (as discussed above). The particularingredients of each cartridge (or compartment) used in a kit can vary inconjunction with the description of the actinic radiation curablepolymeric mixture as previously described.

Rubber Goods

As discussed above, according to the fourth embodiment disclosed herein,a rubber good that is made from (i.e., comprises) a cured polymericproduct resulting from the process of the third embodiment disclosedherein (as described above) is disclosed. As mentioned above,descriptions of the ingredients of the actinic radiation curablepolymeric mixture (and resulting cured polymeric product) apply to thefullest extent possible to certain embodiments of the fourth embodiment,as if fully set forth with specific language directed to the curedpolymeric mixture of the fourth embodiment.

In certain embodiments of the fourth embodiment, the rubber goodcomprising the cured polymeric product comprises at least one of: abushing, a seal, a gasket, a conveyor belt, a hose, or a glove (orgloves). In certain embodiments of the fourth embodiment, the rubbergood comprises a bushing. In certain embodiments of the fourthembodiment, the rubber good comprises a seal. In certain embodiments ofthe fourth embodiment, the rubber good comprises a gasket. In certainembodiments of the fourth embodiment, the rubber good comprises aconveyor belt. In certain embodiments of the fourth embodiment, therubber good comprises a hose. In certain embodiments of the fourthembodiment, the rubber good comprises a glove or gloves.

Manufacturing rubber goods (e.g., bushings, seals, gaskets, conveyorbelts, hoses, or gloves) by an additive manufacturing process using theactinic radiation curable polymeric mixtures disclosed herein oraccording to the processes of the third embodiment disclosed herein canprovide an advantage in terms of being able to produce shapes anddesigns that cannot be produced using traditional manufacturingprocesses such as molding. As a non-limiting example a hose manufacturedby an additive manufacturing process using the actinic radiation curablepolymeric mixtures disclosed herein or according to the processes of thethird embodiment disclosed herein could include internal structure(s)such as multiple channels (to allow separate passage of ingredientsthrough a portion of the hose) or internal projections, protrusions orother internal structure(s) to effect mixing of ingredients during flowthrough the hose. Another non-limiting example includes the ability tomanufacture custom-fitting or custom sized gloves without the need forproduction of a custom form or a multitude of forms in different sizes.

In certain embodiments of the fourth embodiment, the rubber goodcomprises a tire. In certain embodiments of the fourth embodiment, therubber good comprises a tire having at least one component comprised ofa cured polymeric product (e.g., resulting from the processes of thethird embodiment or from use of the cartridge according to the firstembodiment). In certain such embodiments, the component of the tirecomprises at least one of: a tread, a bead, a sidewall, an innerliner,and a subtread. In certain embodiments of the fourth embodiment, thecomponent of the tire comprises a tire tread. In certain embodiments ofthe fourth embodiment, the component of the tire comprises a subtread.In certain embodiments of the fourth embodiment, the component of thetire comprises a tire sidewall. In certain embodiments of the fourthembodiment, the component of the tire comprises a tire bead. In certainembodiments of the fourth embodiment, the component of the tirecomprises a tire innerliner.

Manufacturing a tire component (e.g., treads, beads, sidewalls,innerliners or subtreads) by an additive manufacturing process using theactinic radiation curable polymeric mixtures disclosed herein oraccording to the processes of the third embodiment disclosed herein canprovide an advantage in terms of being able to produce shapes and designthat cannot be produced using traditional manufacturing processes suchas molding. As a non-limiting example, in certain embodiments of thefourth embodiment, wherein the at least one component of the tirecomprises a tread, a tread can be produced that includes at least one ofthe following: a closed hollow void, an undercut void, and an overhungvoid. As used herein, the phrase “closed hollow void” refers to a voidthat is not open to the road-contacting surface of the tread (at leastnot upon manufacture); the particular shape of the closed hollow is notparticularly limited and shapes that are circular, elliptical, square,rectangular, trapezoidal, rectangular, and triangular may be utilized invarious embodiments. Non-limiting examples of closed hollow voids areprovided in FIG. 1. As used herein, the phrase “overhung void” refers toa void that is partially open to the road-contacting surface of thetread (upon manufacture), that is wider (in at least one dimension) thanthe opening, and that includes upper walls (at the road-contactingsurface) having a thickness less than the overall depth of the void andprojecting over and partially covering the opening to theroad-contacting surface of the tread. Non-limiting examples of overhungvoids are provided in FIG. 2. As used herein, the phrase “undercut void”refers to a void that is partially open to the road-contacting surfaceof the tread (upon manufacture), that is wider (in at least onedimension) than the opening, and that includes upper walls (at theroad-contacting surface) that partially extend into the void withouthanging over the void. In certain embodiments, the undercut void hasunsupported walls angled (from the bottom towards the top) generallytoward the opening to the road-contacting surface. In certainembodiments, the overhung void has unsupported walls that aresubstantially parallel (+ or − about 5°) to the road-contacting surfaceor have angles (from the bottom towards the top) generally directed awayfrom the opening to the road-contacting surface. Non-limiting examplesof overhung voids are provided in FIG. 3.

To the extent that the term “includes” or “including” is used in thespecification or the claims, it is intended to be inclusive in a mannersimilar to the term “comprising” as that term is interpreted whenemployed as a transitional word in a claim. Furthermore, to the extentthat the term “or” is employed (e.g., A or B) it is intended to mean “Aor B or both.” When the applicants intend to indicate “only A or B butnot both” then the term “only A or B but not both” will be employed.Thus, use of the term “or” herein is the inclusive, and not theexclusive use. See Bryan A. Garner, A Dictionary of Modern Legal Usage624 (2d. Ed. 1995). Also, to the extent that the terms “in” or “into”are used in the specification or the claims, it is intended toadditionally mean “on” or “onto.” Furthermore, to the extent the term“connect” is used in the specification or claims, it is intended to meannot only “directly connected to,” but also “indirectly connected to”such as connected through another component or components.

While the present application has been illustrated by the description ofembodiments thereof, and while the embodiments have been described inconsiderable detail, it is not the intention of the applicant torestrict or in any way limit the scope of the appended claims to suchdetail. Additional advantages and modifications will readily appear tothose skilled in the art. Therefore, the application, in its broaderaspects, is not limited to the specific details and embodimentsdescribed. Accordingly, departures may be made from such details withoutdeparting from the spirit or scope of the applicant's general inventiveconcept.

This application discloses several numerical range limitations thatsupport any range within the disclosed numerical ranges even though aprecise range limitation is not stated verbatim in the specificationbecause the embodiments could be practiced throughout the disclosednumerical ranges. With respect to the use of substantially any pluraland/or singular terms herein, those having skill in the art cantranslate from the plural to the singular and/or from the singular tothe plural as is appropriate to the context and/or application. Thevarious singular/plural permutations may be expressly set forth hereinfor sake of clarity. As well, all numerical limitations and ranges thatare preceded by the word “about” should be understood to include theparticular number or range without the about as if fully set forthherein.

What is claimed is:
 1. A process for producing a cured polymeric product, comprising providing an additive manufacturing device comprising a source of actinic radiation, an exterior support structure having an atmosphere inside, an interior tank capable of containing a liquid mixture and having an atmosphere above the tank, and an interior support structure, providing to the interior tank a liquid actinic radiation curable polymeric mixture comprising: (i) a polyfunctionalized diene monomer-containing polymer having the formula: [P][F]_(n) where P represents a diene polymer chain, F represents a functional group, n is 2 to about 15, and each F can be the same or different; (ii) optionally a chain extender based upon F or reactive with F; (iii) at least one actinic radiation sensitive photoinitiator; (iv) optionally, a photosensitizer; and (v) a polyfunctional crosslinker reactive with F, repeatedly forming upon the support structure a layer having a thickness of 0.01 mm to 1 mm from the liquid mixture, using actinic radiation to cure each layer, thereby producing a cured polymeric product, wherein at least one of the following has an oxygen level of less than 50 ppm: the liquid actinic radiation curable polymeric mixture within the interior tank, the atmosphere above the liquid actinic radiation curable polymeric mixture within the interior tank, the atmosphere surrounding the interior support structure, or the atmosphere inside the exterior support structure, and wherein the actinic radiation curable polymeric mixture is provided in a cartridge.
 2. The process of claim 1, wherein the cartridge has an oxygen impermeable layer surrounding the liquid actinic radiation curable polymeric mixture.
 3. The process of claim 1, further comprising adding an inert gas to at least one of: the atmosphere above the liquid actinic radiation curable polymeric mixture within the interior tank, the atmosphere surrounding the interior support structure, or the atmosphere inside the exterior support structure.
 4. The process of claim 1, wherein the photosensitizer (iv) is present.
 5. The process of claim 1, wherein the cartridge comprises at least two separate compartments with a first compartment containing (i) and further comprising at least a portion of (ii) when (ii) is present, and a second compartment containing at least one of (iii) or (iv) and further comprising (v) when (v) is present and at least a portion of (ii) when (ii) is present.
 6. The process of claim 1, further comprising adding an inert gas to the cartridge to facilitate providing of the liquid actinic radiation curable polymeric mixture to the interior tank.
 7. The process of claim 1, further comprising removing gas from the cartridge and supplying inert gas to the cartridge as the liquid actinic radiation curable polymeric mixture is removed during forming.
 8. The process of claim 1, wherein the flexible oxygen impermeable layer is surrounded by a rigid outer container which is removable prior to use of the additive manufacturing cartridge.
 9. The process of claim 1, wherein the polyfunctionalized diene monomer-containing polymer comprises a monomer selected the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, farnescene, substituted derivatives of each of the foregoing, and combinations thereof.
 10. The process of claim 1, wherein the polyfunctionalized diene monomer-containing polymer has a Mn of about 3,000 to about 135,000 grams/mole according to a polystyrene standard.
 11. The process of claim 1, wherein F is selected from the group consisting of acrylate, methacrylate, cyanoacrylate, epoxide, aziridine, thioepoxide, and combinations thereof.
 12. The process of claim 1, wherein the polyfunctionalized diene monomer-containing polymer chain further comprises at least one vinyl aromatic monomer.
 13. The process of claim 1, wherein the chain extender of (ii) comprises an (meth)acrylate monomer selected from C2 to C18 alkyl functionalized (meth)acrylates.
 14. The process of claim 1, wherein the photosensitizer of (iv) is selected from the group consisting of a ketocoumarin, a xanthone, a thioxanthone, a polycyclic aromatic hydrocarbon, an oximester derived from aromatic ketone, and combinations thereof.
 15. The process of claim 1, wherein the at least one actinic radiation sensitive photoinitiator of (iii) is selected from the group consisting of a benzophenone, an aromatic α-hydroxyketone, a benzilketal, an aromatic α-aminoketone, a phenylglyoxalic acid ester, a mono-acylphosphinoxide, a bisacylphosphinoxide, and a tris-acylphosphinoxide, and combinations thereof.
 16. The process of claim actinic manufacturing cartridge of claim 1, wherein the polyfunctional crosslinker reactive with F is selected from the group consisting of polyol (meth)acrylates prepared from an aliphatic diol, triol, or tetraol containing 2-100 carbon atoms, polyallylic compounds prepared from an aliphatic diol, triol or tetraol containing 2-100 carbon atoms, polyfunctional amines, and combinations thereof.
 17. The process of claim 1, further comprising forming a rubber good.
 18. The process of claim 17, wherein the rubber good comprises a bushing, a seal, a gasket, a conveyor belt, a hose, or a glove.
 19. The process of claim 17, wherein the rubber good comprises a tire having at least one component selected from a tread, a bead, a sidewall, an innerliner, and a subtread, comprised of the cured polymeric product.
 20. The process of claim 17, wherein the rubber good comprises a tire and the at least one component of the tire comprises a tread comprising at least one of the following: a closed hollow void, an undercut void, or an overhung tread. 